An Efficient One-Pot Synthesis of 5-Sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines as Precursors of 1-Vinylpyrroles

Abstract

Sequential processing of monolithiated tertiary propargylamines with 2-(vinyloxy)ethyl isothiocyanate and t-BuOK–DMSO results in the introduction of a highly reactive 2-(vinyloxy)ethyl group at the position 1 of the pyrrole ring thus formed. In this way, a series of new 5-sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines were obtained in a yield of up to 92%. The latter in the presence of t-BuOK–DMSO system (110–120 °C, 10–15 min) eliminates vinyl alcohol to give rare-functionalized 1-vinylpyrroles, namely 5-sulfanyl-1-vinyl-1H-pyrrol-2-amines, inaccessible by the known methods.

Functionally-substituted pyrroles[1] are widely used in synthetic organic,[2] biological,[3] and medicinal chemistry,[4] as well as in materials science.[5] In particular, pyrroles, bearing amino,[6] alkoxy,[7] sulfanyl,[8] vinyloxy,[9] and vinyl[10] groups, are recommended for the design of new biologically relevant porphyrins, optoelectronic materials, and as synthetically and pharmaceutically important substrates. However, to our knowledge, until recently, general and efficient methods for the direct synthesis of hetero-substituted pyrroles were absent. One of the simplest one-pot approaches to pyrroles having in their structure the above mentioned substituents is based on the reactions of allenic or acetylenic carbanions with isothiocyanates and alkylating agents.[11] Traditional ways to 1-vinylpyrroles are mainly based on the functionalization of preexisting pyrrole ring or structural transformation of the substituents and include the addition of NH-pyrroles to alkynes in the presence of various catalytic systems,[12] indirect vinylation with dihaloalkanes (through substitution-elimination),[13] vinylic substitution with vinyl halides[14] and vinyl triflates,[15] cleavage of 1-[2-(hydroxy)ethyl][16] or 1-[2-(vinyloxy)ethyl][17] substituents, and isomerization of 1-allylic into 1-propen-1-ylic derivatives.[18] Diversely substituted 1-vinylpyrroles were also synthesized in a one-pot directly from ketones and acetylene (via ketoximes) in the superbasic MOH–DMSO (M = Na, K, Cs) systems.[19] But all these methods has both their advantages and disadvantages and limitations. This makes the development of new protocols for the expeditious synthesis of biologically and synthetically relevant functionally and hetero-substituted pyrroles from easily accessible precursors interesting and significant.

Here we report a convenient approach to rare-functionalized 1-vinylpyrroles, based on sequential reaction of monolithiated tertiary propargylamines 1 [N,N-dimethylprop-2-yn-1-amine (1a), N,N-diethylprop-2-yn-1-amine (1b), N,N-dipropylprop-2-yn-1-amine (1c), 1-prop-2-yn-1-ylpyrrolidine (1d), 1-prop-2-yn-1-ylpiperidine (1e), and 4-prop-2-yn-1-ylmorpholine (1f)] with 2-(vinyloxy)ethyl isothiocyanate (2) and alkylating agents (methyl, ethyl, and butyl iodides, allyl and propargyl bromides, bromoacetonitrile, 2-bromomethyl-1,3-dioxolane). 5-Sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines 3 synthesized from these reactants in one preparative step (Table [1], Scheme [1]) were used as precursors of 5-sulfanyl-1-vinyl-1H-pyrrol-2-amines 4, inaccessible by the known methods (Tables 2 and 3).

Table 1 One-Pot Synthesis of 5-Sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines 3 ^a,b

3a (89%,c 77%d)	3b (84%)	3c (79%)
3d (85%,c 80%d)	3e (78%)	3f (69%)
3g (91%)	3h (92%)	3i (90%)
3j (79%)	3k (87%)	3l (91%)

^a Reaction conditions (procedure A): under argon, anhyd THF (20–60 mL), (1) propargylamine 1 (15–60 mmol), n-BuLi (2.5 M solution in hexane, 6.5–24 mL, 16–60 mmol): –70 to –60 → 0–10 °C; (2) CH₂=CHOCH₂CH₂N=C=S (2) (15–50 mmol)/THF (3 mL): 0–10 → 40–48 °C, 5 min; (3) t-BuOK (16–54 mmol)/DMSO (8–28 mL): –40 → 45–55 °C, 5 min; and (4) R¹X (16–104 mmol): 0 → 25–45 °C, 25–60 min.

^b Yield of purified product, isolated by column chromatography or distillation in vacuo (based on isothiocyanate 2).

^c Purified by column chromatography on alumina.

^d Purified by distillation in vacuo.

The cascade reaction leading to pyrroles 3 includes the following steps (procedure A): (1) lithiation of propargylamine 1 with n-BuLi in THF–hexane; (2) addition of formed intermediate A to isothiocyanate; (3) isomerization of acetylenic adduct B into allenic adduct C, accompanied by replacement of lithium cation with potassium (under the action of t-BuOK–DMSO); (4) cyclization of ambident anion C into thienylamide-anion D (at temperature lower than 15 °C); (5) re-cyclization of the latter into pyrrolylsulfide-anion E (at temperature higher than 45 °C); and (6) final S-alkylation of intermediate E (Scheme [1]). Treatment of intermediate D with alkylating agent leads to thiophene 5.

Using this approach, a series of 5-sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines 3 were obtained in 69–92% yields. As can be seen from the data in Table [1], the structure of propargylamine 1 or an alkylating agent does not have too strong effect on the yield of pyrrole 3. But in some cases (to correct the pyrrole yield or to prevent undesirable substituent transformations), slight modifications of the procedure A were made.

Thus, the synthesis of pyrrole 3f from 4-prop-2-yn-1-ylmorpholine (1f) by procedure A leads to a complicated mixture of inseparable products. For this reason, procedure A was slightly changed, namely, before treating the reaction mixture with an alkylating agent, proton donor [t-BuOH (procedure B) or water (procedure C)] was added to it. In the first case, a mixture of pyrrole 3f and thiophene 5f was obtained in a ratio of ca. 80:20, from which pyrrole 3f was isolated in a yield of 59% (Scheme [2]).

This means that under the used reaction conditions, the corresponding potassium thienylamide D is re-cyclized into pyrrolyl sulfide E (precursor of pyrrole 3f) by only 80% (Schemes 1 and 2). But when the duration of treatment of the reaction mixture with the t-BuOK–DMSO system was increased from 5 to 10 minutes, and then water was added (before alkylation), pyrrole 3f was isolated in a yield of 69% as the only reaction product. Thiophene 5f was not identified among the reaction products.

Modified procedure C (with addition of water before alkylation) was also used in the synthesis of pyrroles 3g–j. In the case of allylsulfanyl- and propargylsulfanyl-substituted pyrroles 3i and 3j, the addition of water prevents, respectively, the allyl–propenyl and acetylene–allene isomerization of these substituents.

It was also noted that the yield of the target products rather strongly depends on the method of their isolation. From the results obtained it can be preliminary concluded that purification by column chromatography gives pyrroles 3 in yields higher than by distillation in vacuo. Thus, pyrroles 3a and 3d were isolated by column chromatography in a yield of 89% and 85%, respectively. But when crude products containing these pyrroles were distilled in vacuo, their yields were lower by 12% and 5%, that is, 77% and 80%, respectively (Table [1]).

The structural features of 1-[2-(vinyloxy)ethyl]-substituted pyrroles 3 prompted us to study their chemical behavior, in particular their ability to transformation into 1-vinylpyrroles. Thus, 5-sulfanyl-1-vinyl-1H-pyrrol-2-amines 4, which are not available by traditional methods for construction and functionalization of the pyrrole ring, were obtained in high yield by treatment of compounds 3 with t-BuOK–DMSO system. The reaction proceeds smoothly via elimination of vinyl alcohol from the 1-[2-(vinyloxy)ethyl] substituent and represents a simple and efficient approach to a new family of 1-vinylpyrroles (Tables 2 and 3).

In an initial study, the reaction conditions (amount of the base, temperature, and reaction time) were optimized for the reference reaction of pyrrole 3a with t-BuOK–DMSO system. The results obtained are summarized in Table [2].

Table 2 Screening for Optimal Reaction Conditions for Transformation of 5-Sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines 3 into 5-Sulfanyl-1-vinyl-1H-pyrrol-2-amines 4 via Superbase-Induced Cleavage of C–O Bond

Entry	Substrate	R2N	R1	t-BuOK (equiv)	Temp (°С)	Time (min)	Conversion (%)a of pyrrole 3	Yield (%)b of pyrrole 4
1	3a	Me2N	Me	1.2	r.t.	60	54	48
2	3a	Me2N	Me	2.0	r.t.	60	69	66
3	3a	Me2N	Me	1.1	48–50	20	72	62
4	3a	Me2N	Me	1.2	68–74	20	74	72
5	3a	Me2N	Me	2.0	68–74	20	91	90
6	3a	Me2N	Me	2.0	99–102	20	97	93
7	3a	Me2N	Me	2.0	ca. 112	10	98	98
8	3b	Et2N	Me	2.0	107–110	15	89	85
9	3b	Et2N	Me	2.0	116–119	15	96	87
10	3b	Et2N	Me	2.0c	118–120	15	ca. 3d	0
11	3b	Et2N	Me	2.0e	116–119	15	ca. 14	8
12	3c	Pr2N	Me	2.0	118–120	15	95	97
13	3d		Me	2.0	107–110	15	96	86
14	3d		Me	2.0	115–130	13	99	84
15	3e		Me	2.0	r.t.	60	59	50
16	3e		Me	2.0	107–110	15	99	95
17	3f		Me	2.0	118–120	15	96	88
18	3g	Et2N	Et	2.0	118–120	15	92	80
19	3h	Et2N	n-Bu	2.0	118–120	15	91	91
20	3i	Et2N	CH2=CHCH2	2.0	118–120	15	100	–f
21	3j		HC≡CCH2	2.0	ca. 120	15	100	tar
22	3k	Me2N	N≡CCH2	2.0	r.t.	3 h	100	tar
23	3l	Et2N		2.0	r.t.	60	100	–g
24	3l	Et2N		2.0	108–110	10	78	28
25	3l	Et2N		3.0	ca. 110	10	100	22h

^a Determined by ¹H NMR spectroscopic analysis of the crude reaction mixture.

^b Isolated yields.

^c t-BuONa was used as the base.

^d Starting pyrrole 3b was recovered.

^e KOH was used as the base.

^f A mixture of pyrroles 4i and 3i′ in a ratio of ca. 90:10 was obtained (see Scheme [3]); isolated yield of pyrrole 4i is 47%.

^g Pyrrole 6 was isolated in yield of 68% instead of target 1-vinylpyrrole 4l (see Scheme [4]).

^h A mixture of pyrroles 3b, 4b, and 4l was obtained (see Scheme [5]).

At room temperature [DMSO, t-BuOK (1.2–2.0 equiv), 1 h] the reaction proceeds rather slowly (the conversion of pyrrole 3a is only 54–69%) to give pyrrole 4a in 48–66% yield (Table [2], entries 1 and 2). However, the yield of the target product and conversion of pyrrole 3a increased at higher amount of the base (entries 3–5) and temperature (entries 5–7). The best result was obtained with 2 equivalents of t-BuOK in DMSO at ca. 110 °C for 10 minutes; the yield of pyrrole 4a in this case was excellent (98%) (Table [2], entry 7).

These reaction conditions were then applied to other pyrroles 3 to examine the scope of this protocol to synthesize 1-vinylpyrroles. The latter were obtained by treatment of compounds 3 with t-BuOK (2 equiv)–DMSO at 110–120 °C for 10–15 minutes (Tables 2 and 3), the yields of 5-(alkylsulfanyl)-substituted pyrroles 4a–h reached 80–98% (Table [3]).

Table 3 Superbase-Induced Transformation of 5-Sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines 3 into 5-Sulfanyl-1-vinyl-1H-pyrrol-2-amines 4 ^a

4a (98%)	4b (92%)	4c (97%)
4d (84%)	4e (95%)	4f (88%)
4g (80%)	4h (91%)	4i (47%)
4j (0%)b	4k (0%)b	4l (28%)

^a Yield of purified product, isolated by column chromatography or distillation in vacuo (based on corresponding pyrrole 3).

^b Tar-like material was obtained.

However, treatment of 5-(allylsulfanyl)pyrrole 3i with t-BuOK-DMSO system gave a mixture of 1-vinyl- (4i) and 1-[2-(vinyloxy)ethyl]- (3i′) 5-(prop-1-enylsulfanyl)pyrroles in a ratio of ca. 90:10 (Scheme [3], Table [2], entry 20).

In this case, the elimination of vinyl alcohol is accompanied by base-induced isomerization of the allylsulfanyl group into prop-1-enylsulfanyl, and the rate of isomerization significantly exceeds that of the C–O bond cleavage, as evidenced from the presence of pyrrole 3i′ in the reaction mixture. Pyrrole 4i was isolated in 47% yield as a mixture of E/Z-isomers in a ratio of ca. 1:1 (by ¹H NMR spectroscopic analysis). Similar isomer composition of pyrrole 3i′ was ca. 3:2, yield 6%.

However, we failed to obtain the corresponding 1-vinylpyrroles from pyrroles 3j and 3k containing base-sensitive substituents, such as propargylsulfanyl and cyanomethylsulfanyl groups. In both cases, even upon short-term contact with the superbasic t-BuOK–DMSO system, decomposition and tarring of products were observed.

When pyrrole 3l was treated with 2 equivalents of t-BuOK in DMSO at room temperature for 1 hour, the expected 1-vinylpyrrole 4l was not obtained. Surprisingly, instead 5-{[2-(2-hydroxyethoxy)ethenyl]sulfanyl}-1-[2-(vinyloxy)ethyl]pyrrole (6) was isolated in a yield of 68% (a mixture of E/Z-isomers in a ratio of ca. 60:40) (Scheme [4]).[20]

Formation of pyrrole 6 is explained by the presence of the substituent 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl] in addition to the 1-[2-(vinyloxy)ethyl] group in the structure of pyrrole 3l; a competitive reaction center, as it turned out, also sensitive to the superbasic t-BuOK–DMSO system. Obviously, the SCH₂ group is deprotonated more easily than the NCH₂ group due to the expected stabilization of the formed carbanion center by the neighboring sulfur atom, and also that the C–O bond in the S–C^–HCH–O carbanion fragment generated by potassium tert-butoxide turns out to be significantly weaker than the C–O bond in the carbanionic fragment containing a nitrogen atom in the β-position to the oxygen atom, N–C^–HCH₂–O, which leads to highly selective opening of the dioxolane ring and the formation of compound 6 (Scheme [4]).

When pyrrole 3l reacted with 3 equivalents of t-BuOK in DMSO at ca. 110 °C for 10 minutes, the target 5-[(1,3-dioxolan-2-ylmethyl)sulfanyl]-1-vinylpyrrole 4l (yield 22%) was obtained, however, together with unexpected 5-(methylsulfanyl)-1-vinylpyrrole 4b (yield 14%) and 5-(methylsulfanyl)-1-[2-(vinyloxy)ethyl]pyrrole 3b (yield 3%) (Scheme [5]).

Reaction of pyrrole 3l with 2 equivalents of t-BuOK (under similar conditions) resulted in pyrrole 4l in a yield of 28% as the only reaction product (Table [2], entry 24). Methylsulfanyl-substituted pyrroles 3b and 4b were identified in ¹H NMR spectrum of the reaction mixture in trace amounts.

When pyrrole 6 (the product of the opening of the dioxolane cycle in pyrrole 3l, Scheme [4]) was used, instead of pyrrole 3l, in the reaction depicted in Scheme [5], the same reaction products, that is, pyrroles 3b, 4b, and 4l, were obtained in comparable yields of 4%, 13%, and 21%, respectively. Besides, pyrrole 3l was also identified (yield 2%) among the reaction products.

This means that the reaction of pyrrole 3l with t-BuOK (Scheme [5]) proceeds, first, through the initial opening of the dioxolane cycle to give pyrrole 6, and, secondly, that at ca. 110 °C this reaction (3l → 6) becomes reversible (by analogy with the cyclization of ethyleneglycol monovinyl ether into 2-methyl-1,3-dioxolane in the presence of a base[21]).

The observed formal acetalmethylsulfanyl exchange in the pyrrole ring likely occurs via superbase-catalyzed elimination of pyrrolyl thiolate anion F from the acetal ring-opened product G followed by the methylation of this sulfur-centered anion with DMSO (a well-known methylating agent[22]) to form the methylsulfanyl substituent (Scheme [6]).

The remaining part of the cleaved molecule, acetylenic ether 7, undergoes base-catalyzed auto-oligomerization as a highly reactive species.

It should be noted that in all other cases, when R¹ in pyrrole 3 was not Me, for instance, in SEt, SBu, and SCH₂CH=CH₂-substituted pyrroles 3g–i, 5-(methylsulfanyl)pyrroles 3b and/or 4b were not detected among the reaction products. These results can serve as an additional confirmation of the reaction mechanism presented in Scheme [6], as well as the fact that in this case DMSO is a supplier of a methyl, and not a methylthio group.

We then examined the influence of the nature of the base, using t-BuONa or KOH instead of t-BuOK, in the reaction with pyrrole 3b. However, in the presence of t-BuONa (2 equiv)–DMSO under optimal conditions (118–120 °C, 15 min) satisfactory result was not obtained. The target pyrrole 4b was not identified in the reaction mixture (Table [2], entry 10). The only product was unreacted pyrrole 3b. In the presence of KOH (2 equiv)–DMSO (116–119 °C, 15 min) 1-vinylpyrrole 4b was obtained in the yield of ca. 8% (Table [2], entry 11).

Thus, it is evident that t-BuOK–DMSO system is the most suitable and effective base for the easy and fast transformation of 1-[2-(vinyloxy)ethyl]pyrroles 3 into 1-vinylpyrroles 4 via elimination of vinyl alcohol.

Elemental analysis, IR, NMR (¹H, ¹³C, ¹H–¹H-COSY, ¹H–¹³C-HSQC, ¹H–¹³C-HMBC, ¹H–¹⁵N-HMBC), and mass spectra are consistent with the composition and structure of the compounds 3, 4, and 6.

In conclusion, new concise, facile, and efficient methods for the three-component synthesis of a novel series of 1-[2-(vinyloxy)ethyl]- and 1-vinyl-5-sulfanyl-1H-pyrrol-2-amines have been described. It is shown that 1-[2-(vinyloxy)ethyl]-substituted pyrroles, generated in one preparative step from tertiary propargylamines, 2-(vinyloxy)ethyl isothiocyanate, and alkylating agents in high yields, are easily transformed (under action of t-BuOK–DMSO) into 1-vinylpyrroles with new structures. The synthesized compounds, containing highly reactive and pharmacophoric substituents, are very attractive objects for biological and medicinal research as well as synthons and building blocks for further elaboration of new useful products and materials by simple chemical manipulation involving both the pyrrole core and functional substituents.

Synthesis of employed propargylamines 1 was performed as described by Brandsma.[23] 2-(Vinyloxy)ethyl isothiocyanate (2) was prepared from the 2-(vinyloxy)ethylamine by our earlier reported methods.[24] n-BuLi (2.5 M solution in hexane) and other reagents and solvents are commercially available. All solvents were purified according to standard procedures. All the reactions with n-BuLi were performed under anhydrous conditions in an argon atmosphere. For reactions at low temperatures, a cooling bath with liquid N₂ was used. Reaction courses and products mixtures were monitored by TLC on Merck silica gel 60 F₂₅₄ aluminum sheets; plates were visualized by exposure to I₂ vapor. Column chromatography purifications were carried out on neutral or basic alumina, using hexane, hexane–Et₂O, Et₂O, petroleum ether (PE), PE–Et₂O as eluents.

IR spectra were recorded neat or as KBr pellets on a Bruker Vertex-70 infrared spectrophotometer. ¹H (400.13 MHz), ¹³C (100.62 MHz), ¹⁵N (40.55 MHz), and 2D NMR spectra were recorded with Bruker DPX-400 and AV-400 spectrometers in CDCl₃ at r.t. Chemical shifts are give to the nearest 0.01 ppm (for ¹H) and 0.1 ppm (for ¹³C and ¹⁵N), and are referenced to hexamethyldisiloxane (for ¹H), CDCl₃ (for ¹³C), and MeNO₂ (for ¹⁵N) as an internal standards. Coupling constants are reported to the nearest 0.1 Hz. Spectra were assigned using 2D experiments. The mass spectra (electron impact, 70 eV) were obtained on a Shimadzu GCMS-QP5050A instrument. GC analysis of reaction products was carried out on an Agilent 6890n chromatograph. Microanalyses were carried out with a Flash EA 1112 Series elemental analyzer. Melting points were determined using a SGW X-4 Melting-point apparatus with a microscope.

5-Sulfanyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amines 3; General Procedures A–C

Procedure A

n-BuLi (16–60 mmol) in hexane (6.5–24 mL) was added to a vigorously stirred solution of propargylamine 1 (15–60 mmol) in anhyd THF (20–60 mL) at –70 to –60 °C under argon. The cooling bath was removed, and the temperature was allowed to rise to 0–10 °C. Then a mixture of 2-(vinyloxy)ethyl isothiocyanate (2; 15–50 mmol) and THF (3 mL) was added to the solution in one portion. After stirring for 5 min at 40–48 °C, the reaction mixture was cooled to –40 °C and a solution of t-BuOK (16–54 mmol) in DMSO (8–28 mL) was added. After stirring for 5 min at 45–55 °C, the mixture was cooled (mainly to 0 °C) and alkylating agent (16–104 mmol, 1.0–2.0 equiv) was added. After self-heating to r.t., the solution was stirred at 25–40 °C for 25–60 min, and then quenched with sat. aq NH₄Cl (25–50 mL). The layers were separated, and the products were extracted from the aqueous fraction with Et₂O (3 × 30 mL). The combined organic extracts were washed with sat. aq NH₄Cl (3 × 30 mL), dried (MgSO₄ or K₂CO₃), and concentrated under reduced pressure (on a rotary evaporator, then at ca. 1–2 mmHg) to give a residue from which target pyrrole 3 was isolated by distillation in vacuo or by column chromatography (alumina, hexane, hexane–Et₂O, 10:1, 3:1, 1:1). The yields of the pyrroles 3 were based on isothiocyanate 2.

Procedure B

Similar to procedure A but, after addition of a solution of t-BuOK in DMSO followed by heating at 50–55 °C for 5 min, the reaction mixture was cooled to –10 °C and t-BuOH (3 equiv) and then alkylating agent were added.

Procedure C

Similar to procedure A, but, after addition of a solution of t-BuOK in DMSO followed by heating at 50–58 °C for 5–10 min, the reaction mixture was cooled to –10 °C and H₂O and then alkylating agent were added.

N,N-Dimethyl-5-(methylsulfanyl)-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3a)

(a) Following procedure A [using: THF (30 mL), n-BuLi (2.5 M in hexane; 12 mL, 30.0 mmol), N,N-dimethylprop-2-yn-1-amine (1a; 2.50 g, 30.1 mmol): –65 → 5 °С; isothiocyanate 2 (3.23 g, 25.0 mmol)/THF (3 mL): 5 → 43–45 °С, 5 min; t-BuOK (3.00 g, 26.8 mmol)/DMSO (14 mL): –40 → 45–48 °С, 5 min; MeI (7.00 g, 49.3 mmol, 2.0 equiv): 0 → 27–35 °С, 50 min], pyrrole 3a was obtained in a yield of 5.47 g (crude product: rather pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane); yield: 5.03 g (89%); light-yellow liquid.

(b) Following procedure A [using: THF (60 mL), n-BuLi (2.5 M in hexane; 24 mL, 60.0 mmol), N,N-dimethylprop-2-yn-1-amine (1a; 5.00 g, 60.2 mmol): –65 → 5 °С; isothiocyanate 2 (6.46 g, 50.0 mmol)/THF (3 mL): 0 → 43–45 °С, 5 min; t-BuOK (6.00 g, 53.6 mmol)/DMSO (28 mL): –40 → 45–48 °С, 5 min; MeI (14.2 g, 100.0 mmol, 2.0 equiv): 0 → 35 °С, 25 min], pyrrole 3a was obtained in a yield of 10.76 g (crude product: pure by ¹H NMR analysis); isolated by distillation in vacuo; yield: 8.69 g (77%); light-yellow liquid; purity ca. 100% (GC analysis); bp 96–97 °C/<1 mmHg; n _D ²³ 1.5166.

IR (neat): 3116 (w), 3078 (w), 3045 (w), 2982 (m), 2943 (s), 2920 (s), 2876 (sh), 2855 (m), 2829 (s), 2785 (s), 1637 (s), 1619 (s), 1545 (s), 1474 (sh), 1451 (s), 1426 (s), 1408 (s), 1360 (w), 1317 (s), 1287 (w), 1255 (w), 1200 (s), 1153 (m), 1093 (m), 1084 (sh), 1042 (m), 1018 (m), 1006 (m), 962 (s), 903 (m), 823 (s), 757 (s), 696 (s), 634 (m), 598 (w), 554 (w), 544 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.39 (dd, ³ J_trans = 14.3 Hz, ³ J_{ci s} = 6.8 Hz, 1 H, OCH=CH₂), 6.27 (d, ³ J = 3.6 Hz, 1 H, 4-CH=), 5.74 (d, ³ J = 3.6 Hz, 1 H, 3-CH=), 4.25 (t, ³ J = 6.8 Hz, 2 H, NCH ₂CH₂O), 4.20, 3.98 (dd, ³ J_trans = 14.3 Hz, ³ J_{ci s} = 6.8 Hz, ² J_gem = 2.2 Hz, 2 H, OCH=CH ₂), 3.92 (t, ³ J = 6.8 Hz, 2 H, NCH₂CH ₂O), 2.61 [s, 6 H, N(CH₃)₂], 2.24 (s, 3 H, SCH₃).

¹³C NMR (100 MHz, CDCl₃): δ = 151.3 (OCH=CH₂), 146.8 (C-2), 117.7 (C-5), 115.3 (C-4), 96.6 (C-3), 86.7 (OCH=CH₂), 66.9 (NCH₂ CH₂O), 45.7 [N(CH₃)₂], 41.6 (NCH₂CH₂O), 22.0 (SCH₃).

The ¹H–¹H COSY, ¹H–¹³C HSQC, and ¹H–¹³C HMBC 2D experiments provided additional support for the proposed structure.

¹⁵N NMR (40 MHz, CDCl₃): δ = –224.4 (N_pyrrole), –355.8 [N(CH₃)₂].

MS (EI, 70 eV): m/z (%) = 227 (11, [M + 1]⁺), 226 (77, [M]⁺), 211 (27), 166 (11), 165 (100), 155 (13), 153 (13), 141 (20), 140 (19), 139 (11), 96 (12), 93 (18), 66 (12), 45 (24), 44 (16).

Anal. Calcd for C₁₁H₁₈N₂OS (226.3): C, 58.37; H, 8.02; N, 12.38; S, 14.17. Found: С, 58.30; Н, 7.98; N, 12.33; S, 14.09.

N,N-Diethyl-5-(methylsulfanyl)-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3b)

Following procedure A [using: THF (60 mL), n-BuLi (2.5 M in hexane; 24 mL, 60.0 mmol); N,N-diethylprop-2-yn-1-amine (1b; 6.67 g, 60.0 mmol): –65 → 5 °C; isothiocyanate 2 (6.46 g, 50.0 mmol)/THF (3 mL): 0 → 47–48 °C, 5 min; t-BuOK (6.00 g, 53.6 mmol)/DMSO (23 mL): –40 → 50–52 °C, 5 min; MeI (14.30 g, 100.7 mmol, 2 equiv): 0 → 35 °C, 1 h], pyrrole 3b was obtained in a yield of 12.23 g (crude product); isolated by distillation in vacuo; yield: 10.74 g (84%); light-yellow mobile liquid; purity ca. 100% (GC analysis); bp 116–117 °C/<1 mmHg; n _D ²³ 1.5048.

IR (neat): 3116 (w), 3103 (w), 3078 (w), 3046 (w), 2971 (s), 2922 (s), 2873 (m), 2824 (m), 1637 (s), 1618 (s), 1541 (s), 1473 (sh), 1441 (s), 1405 (s), 1380 (m), 1362 (m), 1328 (sh), 1313 (s), 1294 (m), 1218 (sh), 1200 (s), 1181 (sh), 1168 (sh), 1146 (w), 1129 (w), 1116 (w), 1093 (sh), 1084 (s), 1066 (sh), 1041 (w), 1030 (w), 1006 (m), 964 (s), 947 (sh), 896 (w), 864 (w), 820 (s), 795 (sh), 758 (s), 699 (s), 634 (w), 619 (w), 598 (w), 563 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.41 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.7 Hz, 1 H, OCH=CH₂), 6.30 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.78 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 4.27 (t, ³ J = 6.9 Hz, 2 H, NCH ₂CH₂O), 4.21, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.7 Hz, ² J_gem = 2.1 Hz, 2 H, OCH=CH ₂), 3.90 (t, ³ J = 6.9 Hz, 2 H, NCH₂CH ₂O), 2.87 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 2.24 (s, 3 H, SCH₃), 0.98 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C_Jmod NMR (100 MHz, CDCl₃): δ = 151.6 (OCH=CH₂), 143.4 (C-2), 117.7 (C-5), 115.2 (C-4), 100.0 (C-3), 86.7 (OCH=CH₂), 67.0 (NCH₂ CH₂O), 49.3 [N(CH₂CH₃)₂], 41.2 (NCH₂CH₂O), 22.0 (SCH₃), 12.7 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –220.6 (N_pyrrole), –330.7 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 255 (18, [M + 1]⁺), 254 (97, [M]⁺), 239 (32), 194 (16), 193 (100), 183 (11), 168 (11), 167 (21), 154 (11), 149 (16), 139 (11), 100 (13), 98 (10), 96 (13), 79 (21), 61 (15), 45 (25), 43 (11).

Anal. Calcd for С₁₃H₂₂N₂OS (254.4): С, 61.38; Н, 8.72; N, 11.01; S, 12.60. Found: С, 61.33; Н, 8.68; N, 10.97; S, 12.47.

5-(Methylsulfanyl)-N,N-dipropyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3c)

Following procedure A [using: THF (60 mL), n-BuLi (2.5 M in hexane; 24 mL, 60.0 mmol); N,N-dipropylprop-2-yn-1-amine (1c; 8.35 g, 60.0 mmol): –70 → 7 °C; isothiocyanate 2 (6.46 g, 50.0 mmol)/THF (3 mL): 0 → 45–46 °C, 5 min; t-BuOK (6.00 g, 53.6 mmol)/DMSO (23 mL): –40 → 48–50 C, 5 min; MeI (14.30 g, 100.7 mmol, 2.0 equiv): 0 → 45 °C, 50 min], pyrrole 3c was obtained in a yield of 14.61 g (crude product); isolated by distillation in vacuo; yield: 11.20 g (79%); light-yellow liquid; bp 120–121 °C/<1 mmHg; n _D ²² 1.4976.

IR (neat): 3111 (w), 3045 (w), 2959 (s), 2931 (sh), 2873 (s), 2821 (s), 2736 (w), 1712 (w), 1633 (sh), 1616 (s), 1539 (s), 1459 (s), 1446 (s), 1404 (s), 1384 (sh), 1317 (s), 1200 (s), 1157 (sh), 1086 (s), 1047 (w), 1011 (m), 961 (s), 890 (w), 821 (s), 757 (s), 701 (s), 637 (w), 601 (w), 569 (w), 471 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.41 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.7 Hz, 1 H, OCH=CH₂), 6.29 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.78 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 4.27 (t, ³ J = 7.0 Hz, 2 H, NCH ₂CH₂O), 4.19, 3.98 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.7 Hz, ² J_gem = 2.1 Hz, 2 H, OCH=CH ₂), 3.90 (t, ³ J = 7.0 Hz, 2 H, NCH₂CH ₂O), 2.78–2.74 [m, 4 Н, N(CH ₂CH₂CH₃)₂], 2.25 (s, 3 H, SCH₃), 1.47–1.38 [m, 4 H, N(CH₂CH ₂CH₃)₂], 0.84 [t, ³ J = 7.5 Hz, 6 H, N(CH₂CH₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 151.3 (OCH=CH₂), 144.4 (C-2), 117.4 (C-5), 115.2 (C-4), 99.5 (C-3), 86.7 (OCH=CH₂), 66.9 (NCH₂ CH₂O), 57.7 [N(CH₂CH₂CH₃)₂], 41.2 (NCH₂CH₂O), 22.1 (SCH₃), 20.8 [N(CH₂ CH₂CH₃)₂], 11.6 [N(CH₂CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –220.1 (N_pyrrole), –337.2 [N(C₃H₇)₂].

MS (EI, 70 eV): m/z (%) = 283 (19, [M + 1]⁺), 282 (100, [M]⁺), 267 (50), 222 (12), 221 (96), 181 (13), 177 (11), 168 (10), 163 (13), 139 (12), 112 (10), 100 (16), 96 (10), 61 (14).

Anal. Calcd for С₁₅H₂₆N₂OS (282.4): С, 63.79; Н, 9.28; N, 9.92; S, 11.35. Found: С, 63.63; Н, 9.22; N, 9.91; S, 11.47.

2-(Methylsulfanyl)-5-(pyrrolidin-1-yl)-1-[2-(vinyloxy)ethyl]-1H-pyrrole (3d)

(a) Following procedure A [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); 1-prop-2-yn-1-ylpyrrolidine (1d; 2.18 g, 20.0 mmol): –65 → 10 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 0 → 42–47 °C, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8.5 mL): –40 → 48–50 °C, 5 min; MeI (4.26 g, 30.0 mmol, 2.0 equiv): 0 → 28–35 °C, 35 min], pyrrole 3d was obtained in a yield of 3.69 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane); yield: 3.20 g (85%); light-yellow liquid.

(b) Following procedure A [using: THF (60 mL), n-BuLi (2.5 M in hexane; 24 mL, 60.0 mmol); 1-prop-2-yn-1-ylpyrrolidine (1d; 6.55 g, 60.0 mmol): –65 → 10 °C; isothiocyanate 2 (6.46 g, 50.0 mmol)/THF (3 mL): 0 → 45–47 °C, 5 min; t-BuOK (6.00 g, 53.6 mmol)/DMSO (25 mL): –40 → 48–50 °C, 5 min; MeI (14.80 g, 104.2 mmol, 2.0 equiv): 0 → 36 °C, 25 min], pyrrole 3d was obtained in a yield of 11.80 g (crude product); isolated by distillation in vacuo; yield: 10.08 g (80%); light-yellow mobile liquid; purity ca. 100% (GC analysis); bp 129–131 °C/<1 mmHg; n _D ²² 1.5354.

IR (neat): 3115 (w), 3075 (w), 3043 (w), 2966 (s), 2920 (s), 2875 (s), 2826 (s), 1637 (s), 1618 (s), 1543 (s), 1455 (s), 1409 (s), 1351 (w), 1314 (s), 1292 (sh), 1200 (s), 1146 (w), 1120 (w), 1094 (m), 1082 (m), 1051 (w), 1039 (w), 1019 (sh), 1005 (m), 963 (s), 946 (sh), 901 (m), 822 (s), 750 (s), 686 (m), 625 (w), 608 (w), 598 (w), 562 (w), 489 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.40 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.9 Hz, 1 H, OCH=CH₂), 6.28 (d, ³ J = 3.7 Hz, 1 H, 3-CH=), 5.67 (d, ³ J = 3.7 Hz, 1 H, 4-CH=), 4.26 (t, ³ J = 7.1 Hz, 2 H, NCH ₂CH₂O), 4.21, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.9 Hz, ² J_gem = 2.2 Hz, 2 H, OCH=CH ₂), 3.93 (t, ³ J = 7.1 Hz, 2 H, NCH₂CH ₂O), 3.04–3.01 [m, 4 H, 2′,5′-H, N(CH₂)₄], 2.23 (s, 3 H, SCH₃), 1.89–1.86 [m, 4 H, 3′,4′-H, N(CH₂)₄].

¹³C NMR (100 MHz, CDCl₃): δ = 151.3 (OCH=CH₂), 144.5 (C-5), 117.4 (C-2), 115.6 (C-3), 95.5 (C-4), 86.7 (OCH=CH₂), 66.6 (NCH₂ CH₂O), 53.6 [C-2′, C-5′, N(CH₂)₄], 41.8 (NCH₂CH₂O), 24.6 [C-3′, C-4′, N(CH₂)₄], 22.2 (SCH₃).

The ¹H–¹³C HSQC and ¹H–¹³C HMBC 2D experiments provided additional support for the proposed structure.

¹⁵N NMR (40 MHz, CDCl₃): δ = –224.2 (N_pyrrole), –327.9 [N(CH₂)₄].

MS (EI, 70 eV): m/z (%) = 253 (10, [M + 1]⁺), 252 (78, [M]⁺), 237 (35), 192 (13), 191 (100), 167 (11), 166 (13), 138 (14), 97 (12), 96 (11), 79 (10), 70 (20), 55 (14).

Anal. Calcd for C₁₃H₂₀N₂OS (252.4): C, 61.87; H, 7.99; N, 11.10; S, 12.71. Found: С, 61.73; Н, 7.90; N, 11.08; S, 12.57.

5-(Methylsulfanyl)-2-(piperidin-1-yl)-1-[2-(vinyloxy)ethyl]-1H-pyrrole (3e)

Following procedure A [using: THF (60 mL), n-BuLi (2.5 M in hexane; 24 mL, 60.0 mmol); 1-prop-2-yn-1-ylpiperidine (1e; 7.39 g, 60.0 mmol): –67 → 7 °C; isothiocyanate 2 (6.46 g, 50.0 mmol)/THF (3 mL): 0 → 45–47 °С, 5 min; t-BuOK (6.00 g, 53.6 mmol)/DMSO (25 mL): –40 → 48–52 °C, 5 min; MeI (14.50 g, 102.1 mmol, 2.0 equiv): 0 → 35 °C, 35 min], pyrrole 3e was obtained in a yield of 12.95 g (crude product); isolated by distillation in vacuo; yield: 10.41 g (78%); light-yellow liquid; purity ca. 100% (GC analysis); bp 137–139 °C/<1 mmHg; n _D ²³ 1.5261.

IR (neat): 3116 (w), 3076 (w), 3076 (w), 3045 (w), 2935 (s), 2877 (m), 2853 (s), 2808 (s), 2742 (w), 1637 (sh), 1618 (s), 1542 (s), 1449 (s), 1442 (sh), 1407 (s), 1378 (m), 1361 (w), 1352 (sh), 1320 (s), 1282 (w), 1270 (w), 1260 (w), 1199 (s), 1152 (w), 1142 (w), 1109 (m), 1094 (m), 1082 (sh), 1063 (w), 1045 (w), 1032 (m), 1008 (m), 959 (s), 909 (w), 885 (s), 859 (w), 821 (s), 754 (s), 690 (s), 631 (w), 598 (w), 565 (w), 511 (w), 477 (w), 456 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.39 (dd, ³ J_trans = 14.2 Hz, ³ J_cis = 6.7 Hz, 1 H, OCH=CH₂), 6.27 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.74 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 4.24 (t, ³ J = 6.7 Hz, 2 H, NCH ₂CH₂O), 4.20, 3.99 (dd, ³ J_trans = 14.2 Hz, ³ J_cis = 6.7 Hz, ² J_gem = 2.1 Hz, 2 H, OCH=CH ₂), 3.93 (t, ³ J = 6.7 Hz, 2 H, NCH₂CH ₂O), 2.80–2.77 [m, 4 H, 2′,6′-H, N(CH₂)₅], 2.23 (s, 3 H, SCH₃), 1.66–1.61 [m, 4 H, 3′,5′-H, N(CH₂)₅], 1.55–1.48 [m, 2 H, 4′-H, N(CH₂)₅].

¹³C NMR (100 MHz, CDCl₃): δ = 151.3 (OCH=CH₂), 146.4 (C-2), 117.6 (C-5), 115.2 (C-4), 97.3 (C-3), 86.8 (OCH=CH₂), 67.0 (NCH₂ CH₂O), 54.8 [C-2′, C-6′, N(CH₂)₅], 41.5 (NCH₂CH₂O), 26.3 [C-3′, C-5′, N(CH₂)₅], 24.0 [C-4′, N(CH₂)₅], 22.0 (SCH₃).

¹⁵N NMR (40 MHz, CDCl₃): δ = –223.9 (N_pyrrole), –331.0 [N(CH₂)₅].

MS (EI, 70 eV): m/z (%) = 267 (18, [M + 1]⁺), 266 (93, [M]⁺), 251 (53), 206 (15), 205 (100), 195 (11), 181 (10), 180 (10), 138 (13), 84 (16), 79 (10), 69 (12).

Anal. Calcd for C₁₄H₂₂N₂OS (266.4): C, 63.12; H, 8.32; N, 10.52; S, 12.04. Found: С, 63.02; Н, 8.28; N, 10.51; S, 11.96.

5-(Methylsulfanyl)-2-(morpholin-4-yl)-1-[2-(vinyloxy)ethyl]-1H-pyrrole (3f)

(a) Following procedure B [using: THF (20 mL), n-BuLi (2.5 M in hexane; 6.5 mL, 16.0 mmol); 4-prop-2-yn-1-ylmorpholine (1f; 1.88 g, 15.0 mmol): –60 → 5 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 5 → 42–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8 mL): –40 → 50–55 °C, 5 min; t-BuOH (3.34 g, 45.0 mmol): –10 °C; MeI (4.26 g, 30.0 mmol, 2.0 equiv): 0 °C → r.t., 1 h], pyrrole 3f in a mixture with thiophene 5f (in a ratio of 80:20 by ¹H NMR analysis) was obtained in a yield of 3.90 g (crude product); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1, 3:1); yield: 2.38 g (59%); light-yellow oily liquid; purity ca. 95% (¹H NMR analysis); n _D ²¹ 1.5461 (after additional purification). Isolated yield of thiophene 5f was 15% (0.61 g).

(b) Following procedure C [using: THF (20 mL), n-BuLi (2.5 M in hexane; 6.5 mL, 16.0 mmol); 4-prop-2-yn-1-ylmorpholine (1f; 2.00 g, 16.0 mmol): –60 → 5 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 5 → 42–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8 mL): –40 → 50–57 °C, 10 min; H₂O (2.4 mL): 0 °C; MeI (4.26 g, 30.0 mmol, 2.0 equiv): 0 °C → r.t., 30 min], pyrrole 3f was obtained in a yield of 3.89 g (crude product); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1); yield: 2.78 g (69%).

IR (neat): 3112 (w), 3043 (w), 2955 (s), 2919 (s), 2889 (s), 2851 (s), 2829 (sh), 1618 (s), 1541 (s), 1446 (s), 1409 (m), 1365 (m), 1318 (s), 1261 (m), 1199 (s), 1149 (sh), 1116 (s), 1031 (w), 1009 (w), 962 (m), 919 (w), 890 (m), 823 (s), 758 (s), 688 (m), 629 (w), 585 (w), 549 (w), 485 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.41 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, 1 H, OCH=CH₂), 6.32 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.85 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 4.31 (t, ³ J = 7.0 Hz, 2 H, NCH ₂CH₂O), 4.23, 4.03 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, ² J_gem = 2.3 Hz, 2 H, OCH=CH ₂), 3.98 (t, ³ J = 7.0 Hz, 2 H, NCH₂CH ₂O), 3.78–3.76 (m, 4 H, CH₂OCH₂), 2.88–2.85 (m, 4 H, CH₂NCH₂), 2.27 (s, 3 H, SCH₃).

¹³C NMR (100 MHz, CDCl₃): δ = 151.4 (OCH=CH₂), 144.9 (C-2), 118.5 (C-5), 115.4 (C-4), 98.1 (C-3), 87.0 (OCH=CH₂), 67.3 (CH₂OCH₂), 67.2 (NCH₂ CH₂O), 54.0 (CH₂NCH₂), 41.7 (NCH₂CH₂O), 22.0 (SCH₃).

¹⁵N NMR (40 MHz, CDCl₃): δ = –221.1 (N_pyrrole), –333.4 [N(CH₂)₂O(CH₂)₂].

MS (EI, 70 eV): m/z (%) = 269 (17, [M + 1]⁺), 268 (98, [M]⁺), 253 (56), 208 (17), 207 (100), 197 (11), 182 (11), 138 (18), 96 (16), 83 (12), 45 (21).

Anal. Calcd for C₁₃H₂₀N₂O₂S (268.4): C, 58.18; H, 7.51; N, 10.44; S, 11.95. Found: С, 58.25; H, 7.44; N, 10.51; S, 12.03.

N-Methyl-5-morpholino-N-[2-(vinyloxy)ethyl]thiophen-2-amine (5f) (Tentative Assignment)

¹H NMR (400 MHz, CDCl₃): δ = 6.45 (dd, ³ J_trans = 14.6 Hz, ³ J_cis = 6.9 Hz, 1 H, OCH=CH₂), 5.93 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.72 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 4.15, 3.97 (dd, ³ J_trans = 14.6 Hz, ³ J_cis = 6.9 Hz, ² J_gem = 2.3 Hz, 2 H, OCH=CH ₂), 3.82 (t, ³ J = 5.7 Hz, 2 H, NCH₂CH ₂O), 3.79–3.72 (m, 4 H, CH₂OCH₂), 3.34 (t, ³ J = 5.7 Hz, 2 H, NCH ₂CH₂O), 2.99–2.96 (m, 4 H, CH₂NCH₂), 2.88 (s, 3 H, NCH₃).

¹³C NMR (100 MHz, CDCl₃): δ = 151.7 (OCH=CH₂), 149.2 (C-5), 148.0 (C-2), 107.8 (C-3), 104.4 (C-4), 85.8 (OCH=CH₂), 66.7 (CH₂OCH₂), 65.5 (NCH₂ CH₂O), 55.7 (NCH₂CH₂O), 53.4 (CH₂NCH₂), 47.4 (NCH₃).

MS (EI, 70 eV): m/z (%) = 269 (18, [M + 1]⁺), 268 (100, [M]⁺), 211 (71), 198 (10), 197 (76), 196 (20), 170 (10), 153 (29), 138 (11), 96 (20), 71 (18), 45 (14), 42 (11).

N,N-Diethyl-5-(ethylsulfanyl)-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3g)

Following procedure C [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); N,N-diethylprop-2-yn-1-amine (1b; 2.22 g, 20.0 mmol): –60 → 5 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 5 → 42–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8 mL): –40 → 50–55 °C, 5 min; H₂O (2.4 mL): 0 °C; EtI (4.68 g, 30.0 mmol, 2.0 equiv): 0 °C → r.t., 30 min], pyrrole 3g was obtained in a yield of 4.08 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane); yield: 3.66 g (91%); colorless oily liquid; n _D ²¹ 1.5167.

IR (neat): 3113 (w), 3079 (w), 3049 (w), 2970 (s), 2930 (s), 2873 (s), 2823 (s), 1633 (sh), 1616 (s), 1537 (s), 1465 (sh), 1441 (s), 1404 (s), 1379 (sh), 1315 (m), 1293 (sh), 1199 (s), 1148 (sh), 1084 (m), 1041 (w), 1006 (w), 960 (w), 916 (m), 867 (w), 819 (m), 867 (w), 819 (m), 759 (m), 725 (w), 699 (w), 635 (w), 579 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.41 (dd, ³ J_trans = 14.7 Hz, ³ J_cis = 6.6 Hz, 1 H, OCH=CH₂), 6.32 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.80 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 4.28 (t, ³ J = 7.0 Hz, 2 H, NCH ₂CH₂O), 4.21, 3.98 (dd, ³ J_trans = 14.7 Hz, ³ J_cis = 6.6 Hz, ² J_gem = 2.0 Hz, 2 H, OCH=CH ₂), 3.88 (t, ³ J = 7.0 Hz, 2 H, NCH₂CH ₂O), 2.87 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 2.57 (q, ³ J = 7.4 Hz, 2 H, SCH ₂CH₃), 1.15 (t, ³ J = 7.4 Hz, 3 H, SCH₂CH ₃), 0.98 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C_Jmod NMR (100 MHz, CDCl₃): δ = 151.6 (OCH=CH₂), 143.8 (C-2), 113.8 (C-5), 115.5 (C-4), 100.1 (C-3), 86.9 (OCH=CH₂), 67.2 (NCH₂ CH₂O), 49.6 [N(CH₂CH₃)₂], 41.3 (NCH₂CH₂O), 32.1 (SCH₂CH₃), 14.6 (SCH₂ CH₃), 12.9 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –217.2 (N_pyrrole), –330.2 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 269 (14, [M + 1]⁺), 268 (76, [M]⁺), 239 (61), 194 (18), 193 (100), 168 (12), 167 (20).

Anal. Calcd for C₁₄H₂₄N₂OS (268.4): C, 62.64; H, 9.01; N, 10.44; S, 11.95. Found: C, 62.55; H, 9.10; N, 10.52; S, 11.81.

5-(Butylsulfanyl)-N,N-diethyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3h)

Following procedure C [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); N,N-diethylprop-2-yn-1-amine (1b; 2.22 g, 20.0 mmol): –60 → 5 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 5 → 42–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8 mL): –40 → 50–58 °C, 5 min; H₂O (2.4 mL): 0 °C; n-BuI (5.52 g, 30.0 mmol, 2.0 equiv): 0 °C → r.t., 30 min, and 40 °C, 1–2 min], pyrrole 3h was obtained in a yield of 4.66 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane); yield: 4.09 g (92%); colorless oily liquid; n _D ²¹ 1.5102.

IR (neat): 3113 (w), 3075 (w), 3046 (w), 2964 (s), 2930 (s), 2870 (s), 2824 (sh), 1634 (sh), 1616 (s), 1539 (s), 1444 (s), 1404 (m), 1379 (m), 1314 (s), 1293 (sh), 1199 (s), 1151 (sh), 1086 (m), 1042 (w), 1007 (w), 960 (m), 916 (w), 819 (s), 759 (s), 699 (m), 638 (w), 602 (sh), 563 (w), 467 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.41 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, 1 H, OCH=CH₂), 6.30 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.79 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 4.21 (t, ³ J = 7.1 Hz, 2 H, NCH ₂CH₂O), 4.21, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, ² J_gem = 2.0 Hz, 1 H, OCH=CH ₂), 3.88 (t, ³ J = 7.1 Hz, 2 H, NCH₂CH ₂O), 2.86 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 2.56 (t, ³ J = 7.3 Hz, 2 H, SCH₂C₃H₇), 1.53–1.41 (m, 2 H, SCH₂CH ₂C₂H₅), 1.39–1.32 [m, 2 H, S(CH₂)₂CH ₂CH₃], 0.98 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂], 0.86 [t, ³ J = 7.3 Hz, 3 H, S(CH₂)₃CH ₃].

¹³C_Jmod NMR (100 MHz, CDCl₃): δ = 151.6 (OCH=CH₂), 143.7 (C-2), 116.8 (C-4), 115.9 (C-5), 100.1 (C-3), 86.9 (OCH=CH₂), 67.1 (NCH₂ CH₂O), 49.6 [N(CH₂CH₃)₂], 41.3 (NCH₂CH₂O), 38.0 (SCH₂C₃H₇), 31.6 (SCH₂ CH₂C₂H₅), 21.8 [S(CH₂)₂ CH₂CH₃], 13.8 [S(CH₂)₃ CH₃], 12.9 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –217.4 (N_pyrrole), –330.1 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 297 (7, [M + 1]⁺), 296 (37, [M]⁺), 239 (51), 194 (13), 193 (100), 167 (17), 96 (13), 61 (11).

Anal. Calcd for C₁₆H₂₈N₂OS (296.5): C, 64.82; H, 9.52; N, 9.45; S, 10.82. Found: C, 65.01; H, 9.49; N, 9.38; S, 10.77.

5-(Allylsulfanyl)-N,N-diethyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3i)

Following procedure C [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); N,N-diethylprop-2-yn-1-amine (1b; 2.22 g, 20.0 mmol): –60 → 5 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 5 → 42–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8 mL): –40 → 50–55 °C, 5 min; H₂O (2.4 mL): 0 °C; CH₂=CHCH₂Br (3.63 g, 30.0 mmol, 2.0 equiv): 0 °C → r.t., 1 h], pyrrole 3i was obtained in a yield of 4.26 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane); yield: 3.79 g (90%); colorless oily liquid; n _D ²¹ 1.5260.

IR (neat): 3113 (w), 3074 (w), 3046 (w), 2969 (s), 2928 (s), 2871 (s), 2824 (s), 1633 (sh), 1616 (s), 1539 (s), 1470 (sh), 1445 (s), 1404 (m), 1377 (m), 1315 (m), 1292 (sh), 1258 (w), 1199 (s), 1151 (sh), 1086 (m), 1039 (w), 1007 (w), 962 (m), 896 (w), 820 (s), 759 (s), 699 (m), 638 (w), 602 (sh), 563 (w), 463 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.44 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.5 Hz, 1 H, OCH=CH₂), 6.37 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.83 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 5.83 (ddt, ³ J_trans = 17.1 Hz, ³ J_cis = 10.0 Hz, ³ J = 7.4 Hz, 1 H, SCH₂CH=CH₂), 4.96, 4.86 (br dd, ³ J_trans = 17.1 Hz, ³ J_cis = 10.0 Hz, 2 H, SCH₂CH=CH ₂), 4.31 (t, ³ J = 7.0 Hz, 2 H, NCH ₂CH₂O), 4.24, 4.02 (br dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.5 Hz, 2 H, OCH=CH ₂), 3.90 (t, ³ J = 7.0 Hz, 2 H, NCH₂CH ₂O), 3.21 (d, ³ J = 7.4 Hz, 2 H, SCH ₂CH=CH₂), 2.89 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 0.99 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C_Jmod NMR (100 MHz, CDCl₃): δ = 151.6 (OCH=CH₂), 143.9 (C-2), 134.1 (SCH₂ CH=CH₂), 117.7 (SCH₂CH=CH₂), 117.2 (C-4), 115.0 (C-5), 100.2 (C-3), 86.9 (OCH=CH₂), 67.2 (NCH₂ CH₂O), 49.7 [N(CH₂CH₃)₂], 41.4 (NCH₂CH₂O), 42.0 (SCH₂CH=CH₂), 12.9 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –217.0 (N_pyrrole), –329.4 [N(C₂H₅)₂].

Anal. Calcd for C₁₅H₂₄N₂OS (280.4): C, 64.24; H, 8.63; N, 9.99; S, 11.43. Found: C, 64.30; H, 8.70; N, 9.85; S, 11.33.

2-(Prop-2-ynylsulfanyl)-5-(pyrrolidin-1-yl)-1-[2-(vinyloxy)ethyl]-1H-pyrrole (3j)

Following procedure C [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); 1-prop-2-ynylpyrrolidine (1d; 2.10 g, 20.0 mmol): –60 → 10 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 10 → 42–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8 mL): –40 → 50–55 °C, 5 min; H₂O (4.2 mL): –10 °C; HC≡CCH₂Br (3.57 g, 30.0 mmol, 2.0 equiv): 0 °C → r.t., 1 h], pyrrole 3j was obtained in a yield of 4.33 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane); yield: 3.27 g (79%); pinkish oily liquid; n _D ²² 1.5637.

IR (neat): 3291 (s) (HC≡), 3113 (w), 3039 (sh), 2963 (s), 2874 (s), 2827 (s), 2116 (w) (C≡C), 1634 (sh), 1618 (s), 1540 (s), 1454 (s), 1409 (m), 1353 (w), 1316 (s), 1198 (s), 1119 (w), 1086 (m), 1049 (w), 1008 (m), 959 (m), 900 (m), 823 (s), 752 (s), 681 (sh), 640 (s), 563 (w), 492 (w), 462 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.44 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 6.39 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.9 Hz, 1 H, OCH=CH₂), 5.69 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 4.33 (t, ³ J = 6.8 Hz, 2 H, NCH ₂CH₂O), 4.21, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.9 Hz, ² J_gem = 2.2 Hz, 2 H, OCH=CH ₂), 3.93 (t, ³ J = 6.8 Hz, 2 H, NCH₂CH ₂O), 3.29 (d, ⁴ J = 2.6 Hz, 2 H, SCH₂), 3.05–3.02 (m, 4 H, 2′,5′-CH₂), 2.23 (t, ⁴ J = 2.6 Hz, 1 H, HC≡), 1.89–1.86 (m, 4 H, 3′,4′-CH₂).

¹³C NMR (100 MHz, CDCl₃): δ = 151.4 (OCH=CH₂), 145.8 (C-5), 118.7 (C-3), 114.2 (C-2), 95.9 (C-4), 87.0 (OCH=CH₂), 80.3 (C≡), 72.2 (HC≡), 66.7 (NCH₂ CH₂O), 53.4 (C-2′, C-5′), 42.3 (NCH₂CH₂O), 27.2 (SCH₂), 24.8 (C-3′, C-4′).

¹⁵N NMR (40 MHz, CDCl₃): δ = –222.0 (N_pyrrole), –324.7 [N(CH₂)₄].

MS (EI, 70 eV): m/z (%) = 276 (17, [M]⁺), 239 (10), 238 (27), 237 (100), 192 (18), 191 (95), 167 (18), 166 (17), 138 (20), 96 (17), 70 (21), 45 (15), 39 (19).

Anal. Calcd for C₁₅H₂₀N₂OS (276.4): C, 65.18; H, 7.29; N, 10.14; S, 11.60. Found: C, 65.40; H, 7.19; N, 10.01; S, 11.38.

5-(Cyanomethylsulfanyl)-N,N-dimethyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3k)

Following procedure A [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); N,N-dimethylprop-2-yn-1-amine (1a; 2.10 g, 25.3 mmol): –60 → 0 °C; isothiocyanate 2 (1.94 g, 15.0 mmol)/THF (3 mL): 5 → 40–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8.5 mL): –40 → 48–54 °C, 5 min; BrCH₂CN (3.71 g, 30.9 mmol, 2.0 equiv): –30 °C → r.t., 30 min], pyrrole 3k was obtained in a yield of 4.19 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 1:1); yield: 3.28 g (87%); brownish oily liquid; n _D ²¹ 1.5440.

IR (neat): 3166 (w), 3114 (w), 3040 (sh), 2976 (sh), 2945 (s), 2874 (sh), 2859 (s), 2833 (sh), 2788 (s), 2243 (s) (C≡N), 1621 (s), 1542 (s), 1455 (s), 1421 (s), 1360 (m), 1319 (s), 1254 (sh), 1195 (s), 1149 (sh), 1088 (m), 1040 (m), 1015 (m), 961 (m), 902 (m), 826 (m), 763 (m), 699 (m), 632 (w), 602 (sh), 547 (w), 492 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.55 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 6.34 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, 1 H, OCH=CH₂), 5.82 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 4.32 (t, ³ J = 6.0 Hz, 2 H, NCH ₂CH₂O), 4.17, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, ² J _gem = 2.2 Hz, 2 Н, OCH=CH ₂), 3.93 (t, ³ J = 6.0 Hz, 2 H, NCH₂CH ₂O), 3.30 (s, 2 Н, SCH₂), 2.63 [s, 6 Н, N(CH₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 151.1 (OCH=CH₂), 148.6 (C-2), 119.8 (C-4), 116.8 (C≡N), 111.7 (C-5), 97.8 (C-3), 87.0 (OCH=CH₂), 66.9 (NCH₂ CH₂O), 45.3 [N(CH₃)₂], 42.1 (NCH₂CH₂O), 24.0 (SCH₂).

¹⁵N NMR (40 MHz, CDCl₃): δ = –130.9 (C≡N), –223.5 (N_pyrrole), –355.0 [N(CH₃)₂].

MS (EI, 70 eV): m/z (%) = 251 (7, [M]⁺), 211 (100), 165 (81).

Anal. Calcd for С₁₂Н₁₇N₃OS (251.3): С, 57.34; Н, 6.82; N, 16.72; S, 12.76. Found: С, 57.28; Н, 6.81; N, 16.67; S, 12.64.

5-[(1,3-Dioxolan-2-ylmethyl)sulfanyl]-N,N-diethyl-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3l)[20]

Following procedure A [using: THF (20 mL), n-BuLi (2.5 M in hexane; 7 mL, 17.5 mmol); N,N-diethylprop-2-yn-1-amine (1b; 2.20 g, 19.8 mmol): –60 → 0 °С; isothiocyanate 2 (1.95 g, 15.1 mmol)/THF (3 mL): 0 → 40–45 °С, 5 min; t-BuOK (1.80 g, 16.0 mmol)/DMSO (8.5 mL): –40 → 50–55 °С, 5 min; 2-(bromomethyl)-1,3-dioxolane (2.63 g, 15.7 mmol, 1.0 equiv): 0 → 25–40 °С, 1 h], pyrrole 3l was obtained in a yield of 4.91 g (crude product: pure by ¹H NMR analysis); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1, 3:1); yield: 4.46 g (91%); pinkish oily liquid; n _D ²² 1.5251.

IR (neat): 3110 (w), 2969 (s), 2931 (s), 2881 (s), 2825 (sh), 1618 (s), 1538 (s), 1445 (s), 1403 (s), 1381 (sh), 1316 (s), 1197 (s), 1133 (s), 1089 (sh), 1037 (s), 968 (s), 950 (sh), 820 (s), 760 (s), 700 (m), 639 (w), 563 (w), 463 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 6.41 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.8 Hz, 1 H, OCH=CH₂), 6.36 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.78 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 4.98 (t, ³ J = 4.7 Hz, 1 H, ОCHО), 4.31 (t, ³ J = 6.8 Hz, 2 H, NCH ₂CH₂O), 4.20, 3.97 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.8 Hz, ² J_gem = 2.1 Hz, 2 H, OCH=CH ₂), 3.89 (t, ³ J = 6.8 Hz, 2 H, NCH₂CH ₂O), 3.98–3.94, 3.87–3.83 (both m, 4 H, OCH₂CH₂O), 2.86 [q, ³ J = 7.1 Hz, 4 H, N(CH ₂CH₃)₂], 2.77 (d, ³ J = 4.7 Hz, 2 H, SCH₂), 0.97 [t, ³ J = 7.1 Hz, 6 H, N(CH₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 151.6 (OCH=CH₂), 144.0 (C-2), 117.4 (C-4), 115.0 (C-5), 103.2 (ОCHО), 100.4 (C-3), 86.9 (OCH=CH₂), 67.1 (NCH₂ CH₂O), 65.3 (OCH₂CH₂О), 49.6 [N(CH₂CH₃)₂], 41.6 (NCH₂CH₂O), 41.5 (SCH₂), 12.9 [N(CH₂ CH₃)₂].

The ¹H–¹H COSY, ¹H–¹³C HSQC, and ¹H–¹³C HMBC 2D experiments provided additional support for the proposed structure.

¹⁵N NMR (40 MHz, CDCl₃): δ = –200.3 (N_pyrrole), –332.8 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 327 (12, [M + 1]⁺), 326 (59, [M]⁺), 240 (13), 239 (57), 207 (11), 194 (12), 193 (100), 167 (21), 138 (10), 137 (19), 96 (10), 79 (13), 73 (20), 45 (33), 43 (22).

Anal. Calcd for C₁₆H₂₆N₂O₃S (326.5): C, 58.87; H, 8.03; N, 8.58; S, 9.82. Found: C, 58.77; H, 7.88; N, 8.43; S, 9.71.

5-Sulfanyl-1-vinyl-1H-pyrrol-2-amines 4; General Procedure

1-[2-(Vinyloxy)ethyl]pyrrole 3 (2.5–10 mmol) was added to a solution of t-BuOK (5–20 mmol, 2 equiv) in DMSO (1.5–6 mL) at 110–130 °C. The reaction mixture was stirred at this temperature for 10–15 min, cooled to r.t., diluted with H₂O (10 mL) and extracted with Et₂O (5 × 5 mL). The combined organic layers were washed with H₂O (3 × 5 mL), dried (MgSO₄) and concentrated under reduced pressure. The residue that contained 1-vinylpyrrole 4 was purified by column chromatography (neutral alumina, hexane, PE, PE–Et₂O 10:1) or by distillation in vacuo.

N,N-Dimethyl-5-(methylsulfanyl)-1-vinyl-1H-pyrrol-2-amine (4a)

Following the general procedure [using: DMSO (1.5 mL); t-BuOK (0.56 g, 5.0 mmol, 2 equiv), pyrrole 3a (0.57 g, 2.5 mmol): ca. 112 °C, 10 min], 1-vinylpyrrole 4a was obtained in a yield of 0.48 g (crude product); isolated by column chromatography (alumina, PE, PE–Et₂O 10:1); yield: 0.45 g (98%); purity 97% (¹H NMR analysis); additionally purified by distillation in vacuo; yellowish liquid; purity ca. 100% (GC analysis); bp 69–71 °C/<1 mmHg; n _D ²³ 1.5532.

IR (neat): 3109 (w), 3037 (w), 2986 (m), 2946 (m), 2918 (m), 2860 (m), 2831 (m), 2787 (m), 1640 (s), 1554 (s), 1486 (m), 1453 (m), 1428 (s), 1401 (s), 1335 (m), 1310 (m), 1281 (m), 1238 (m), 1205 (w), 1177 (w), 1153 (w), 1097 (w), 1049 (m), 1008 (m), 979 (m), 960 (m), 901 (m), 883 (m), 760 (m), 716 (m), 702 (m), 615 (w), 594 (w), 547 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.09 (dd, ³ J_trans = 16.4 Hz, ³ J_cis = 9.4 Hz, 1 H, NCH=CH₂), 6.26 (d, ³ J = 3.6 Hz, 1 H, 4-CH=), 5.80, 4.91 (dd, ³ J_trans = 16.4 Hz, ³ J_cis = 9.4 Hz, 2 H, NCH=CH ₂), 5.59 (d, ³ J = 3.6 Hz, 1 H, 3-CH=), 2.61 [s, 6 H, N(CH₃)₂], 2.19 (s, 3 H, SCH₃).

¹³C NMR (100 MHz, CDCl₃): δ = 147.7 (C-2), 129.8 (NCH=CH₂), 118.3 (C-5), 116.7 (C-4), 103.1 (NCH=CH₂), 95.0 (C-3), 44.2 [N(CH₃)₂], 21.1 (SCH₃).

The ¹H–¹³C HMBC 2D experiment provided additional support for the proposed structure.

¹⁵N NMR (40 MHz, CDCl₃): δ = –211.6 (N_pyrrole), –347.7 [N(CH₃)₂].

MS (EI, 70 eV): m/z (%) = 183 (11, [M + 1]⁺), 182 (100, [M]⁺), 167 (97), 140 (23), 135 (21), 133 (11), 126 (14), 124 (21), 123 (55), 96 (13), 93 (15), 82 (15), 66 (13), 42 (16).

Anal. Calcd for C₉H₁₄N₂S (182.3): C, 59.30; H, 7.74; N, 15.37; S, 17.59. Found: C, 59.15; H, 7.69; N, 15.30; S, 17.55.

N,N-Diethyl-5-(methylsulfanyl)-1-vinyl-1H-pyrrol-2-amine (4b)

Following the general procedure [using: DMSO (6 mL); t-BuOK (2.24 g, 20.0 mmol, 2 equiv), pyrrole 3b (2.54 g, 10.0 mmol): 116–119 °C, 15 min], 1-vinylpyrrole 4b was obtained in a yield of 2.04 g (crude product); isolated by column chromatography (alumina, PE, PE–Et₂O 10:1); yield: 1.93 g (92%); purity 94% (¹H NMR analysis)]; additionally purified by distillation in vacuo: light-yellow mobile liquid; purity ca. 100% (GC analysis); bp ca. 96 °C/<1 mmHg; n _D ²³ 1.5297.

IR (neat): 3107 (w), 3078 (w), 3036 (w), 2972 (s), 2932 (sh), 2920 (s), 2871 (m), 2846 (m), 2826 (m), 2755 (w), 2725 (w), 1640 (s), 1550 (s), 1479 (m), 1463 (s), 1448 (m), 1400 (s), 1388 (sh), 1364 (sh), 1337 (m), 1304 (m), 1280 (m), 1247 (w), 1226 (m), 1194 (sh), 1184 (w), 1163 (m), 1115 (w), 1086 (m), 1069 (m), 1026 (w), 1016 (sh), 1004 (w), 979 (sh), 968 (s), 950 (w), 919 (w), 880 (s), 836 (w), 807 (w), 788 (m), 763 (s), 714 (m), 657 (w), 625 (w), 594 (w), 560 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.12 (dd, ³ J_trans = 16.4 Hz, ³ J_cis = 9.7 Hz, 1 H, NCH=CH₂), 6.27 (d, ³ J = 3.6 Hz, 1 H, 4-CH=), 5.85, 4.85 (dd, ³ J_trans = 16.4 Hz, ³ J_cis = 9.7 Hz, 2 H, NCH=CH ₂), 5.69 (d, ³ J = 3.6 Hz, 1 H, 3-CH=), 2.90 [q, ³ J = 7.4 Hz, 4 H, N(СН ₂CH₃)₂], 2.21 (s, 3 H, SCH₃), 0.97 [t, ³ J = 7.4 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 144.2 (C-2), 130.0 (NCH=CH₂), 118.0 (C-5), 116.5 (C-4), 102.6 (NCH=CH₂), 99.6 (C-3), 47.8 [N(CH₂CH₃)₂], 20.9 (SCH₃), 12.0 [N(CH₂ CH₃)₂].

Anal. Calcd for C₁₁H₁₈N₂S (210.3): C, 62.81; H, 8.63; N, 13.32; S, 15.24. Found: C, 62.90; H, 8.70; N, 13.18; S, 15.18.

5-(Methylsulfanyl)-N,N-dipropyl-1-vinyl-1H-pyrrol-2-amine (4c)

Following the general procedure [using: DMSO (6 mL); t-BuOK (2.24 g, 20.0 mmol, 2 equiv), pyrrole 3c (2.84 g, 10.0 mmol): 118–120 °C, 15 min], 1-vinylpyrrole 4c was obtained in a yield of 2.37 g (crude product); isolated by column chromatography (alumina, PE, PE–Et₂O, 10:1); yield: 2.31 g (97%); purity 94% (¹H NMR analysis); additionally purified by distillation in vacuo: colorless liquid; purity ca. 100% (GC analysis); bp ca. 116 °C/1 mmHg; n _D ²² 1.5200.

IR (neat): 3107 (w), 3078 (w), 3036 (w), 2960 (s), 2933 (s), 2920 (s), 2873 (m), 2824 (m), 2735 (w), 1640 (s), 1550 (s), 1475 (sh), 1465 (sh), 1457 (m), 1400 (s), 1390 (s), 1337 (w), 1310 (w), 1290 (m), 1261 (w), 1243 (w), 1193 (w), 1180 (w), 1161 (w), 1081 (m), 1022 (w), 1011 (w), 981 (m), 965 (m), 923 (w), 880 (m), 837 (sh), 762 (m), 717 (m), 640 (w), 618 (w), 563 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.12 (dd, ³ J_trans = 16.3 Hz, ³ J_cis = 9.7 Hz, 1 H, NCH=CH₂), 6.26 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.83, 4.85 (dd, ³ J_trans = 16.3 Hz, ³ J_cis = 9.7 Hz, 2 H, NCH=CH ₂), 5.68 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 2.81–2.78 [m, 4 Н, N(CH ₂CH₂CH₃)₂], 2.21 (s, 3 H, SCH₃), 1.43 [sext, ³ J = 7.4 Hz, 4 H, N(CH₂CH ₂CH₃)₂], 0.82 [t, ³ J = 7.4 Hz, 6 H, N(CH₂CH₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 145.0 (C-2), 130.0 (NCH=CH₂), 117.9 (C-5), 116.6 (C-4), 102.8 (NCH=CH₂), 99.2 (C-3), 56.3 [N(CH₂CH₂CH₃)₂], 20.9 (SCH₃), 20.2 [N(CH₂ CH₂CH₃)₂], 11.6 [N(CH₂CH₂ CH₃)₂].

Anal. Calcd for C₁₃H₂₂N₂S (238.4): C, 65.50; H, 9.30; N, 11.75; S, 13.45. Found: C, 65.58; H, 9.33; N, 11.65; S, 13.38.

2-(Methylsulfanyl)-5-(pyrrolidin-1-yl)-1-vinyl-1H-pyrrole (4d)

Following the general procedure [using: DMSO (6 mL); t-BuOK (2.24 g, 20.0 mmol, 2 equiv), pyrrole 3d (2.55 g, 10.1 mmol): 115–130 °C, 13 min], 1-vinylpyrrole 4d was obtained in a yield of 2.01 g (crude product); isolated by column chromatography (alumina, PE, PE–Et₂O, 10:1); yield: 1.76 g (84%); additionally purified by distillation in vacuo: colorless liquid; purity ca. 100% (GC analysis); bp 108–111°C/<1 mmHg; n _D ²² 1.5721.

IR (neat): 3108 (w), 3034 (w), 2968 (m), 2918 (m), 2875 (m), 2824 (m), 1640 (s), 1552 (s), 1476 (m), 1463 (sh), 1407 (s), 1393 (sh), 1351 (w), 1335 (w), 1306 (m), 1279 (w), 1233 (w), 1196 (w), 1122 (w), 1081 (w), 1061 (w), 1022 (w), 1011 (w), 983 (m), 964 (m), 897 (m), 886 (m), 829 (w), 752 (m), 711 (w), 698 (w), 671 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.05 (dd, ³ J_trans = 16.4 Hz, ³ J_cis = 9.4 Hz, 1 H, NCH=CH₂), 6.27 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 5.67, 4.94 (dd, ³ J_trans = 16.4 Hz, ³ J_cis = 9.4 Hz, 2 H, NCH=CH ₂), 5.55 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 3.03–3.01 [nr m, 4 H, 2′,5′-H, N(CH₂)₄], 2.19 (s, 3 H, SCH₃), 1.86–1.85 [nr m, 4 H, 3′,4′-H, N(CH₂)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 145.4 (C-5), 130.3 (NCH=CH₂), 117.6 (C-2), 117.0 (C-4), 103.8 (C-3), 93.8 (NCH=CH₂), 52.0 [C-2′, C-5′, N(CH₂)₄], 24.3 [C-3′, C-4′, N(CH₂)₄], 21.2 (SCH₃).

Anal. Calcd for C₁₁H₁₆N₂S (208.3): C, 63.42; H, 7.74; N, 13.45; S, 15.39. Found: C, 63.28; H, 7.80; N, 13.38; S, 15.45.

5-(Methylsulfanyl)-2-(piperidin-1-yl)-1-vinyl-1H-pyrrole (4e)

Following the general procedure [using: DMSO (6 mL); t-BuOK (2.24 g, 20.0 mmol, 2 equiv), pyrrole 3e (2.66 g, 10.0 mmol): 107–112 °C, 15 min], 1-vinylpyrrole 4e was obtained in a yield of 2.19 g (crude product); isolated by column chromatography (alumina, PE, PE–Et₂O, 10:1); yield: 2.16 g (95%); colorless liquid; purity 98% (¹H NMR analysis); bp ca. 124 °C/<1 mmHg; n _D ²⁰ 1.5630.

IR (neat): 3108 (w), 3075 (w), 3036 (w), 2935 (s), 2922 (s), 2852 (s), 2809 (s), 2745 (w), 2700 (w), 2670 (w), 1639 (s), 1553 (s), 1477 (s), 1466 (s), 1452 (s), 1442 (m), 1405 (s), 1392 (s), 1380 (m), 1352 (w), 1335 (m), 1315 (m), 1283 (m), 1272 (m), 1258 (m), 1238 (m), 1210 (m), 1183 (w), 1154 (w), 1139 (w), 1110 (m), 1084 (w), 1064 (m), 1033 (m), 1004 (m), 981 (m), 970 (m), 954 (m), 910 (w), 882 (s), 862 (m), 830 (w), 811 (w), 758 (s), 709 (m), 699 (sh), 681 (m), 649 (w), 618 (w), 573 (w), 513 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.13 (dd, ³ J_trans = 16.3 Hz, ³ J_cis = 9.7 Hz, 1 H, NCH=CH₂), 6.26 (d, ³ J = 3.6 Hz, 1 H, 4-CH=), 5.86, 4.86 (dd, ³ J_trans = 16.3 Hz, ³ J_cis = 9.7 Hz, 2 H, NCH=CH ₂), 5.58 (d, ³ J = 3.6 Hz, 1 H, 3-CH=), 2.81 [br t, ³ J = 5.0 Hz, 4 H, 2′,6′-H, N(CH₂)₅], 2.18 (s, 3 H, SCH₃), 1.66–1.60 [m, 4 H, 3′,5′-H, N(CH₂)₅], 1.55–1.48 [m, 2 H, 4′-H, N(CH₂)₅].

¹³C NMR (100 MHz, CDCl₃): δ = 147.6 (C-2), 129.9 (NCH=CH₂), 118.3 (C-5), 116.8 (C-4), 102.2 (NCH=CH₂), 95.6 (C-3), 53.4 [C-2′, C-6′, N(CH₂)₅], 25.8 [C-3′, C-5′, N(CH₂)₅], 24.0 [C-4′, N(CH₂)₅], 20.1 (SCH₃).

Anal. Calcd for C₁₂H₁₈N₂S (222.4): C, 64.82; H, 8.16; N, 12.60; S, 14.42. Found: C, 64.91; H, 8.23; N, 12.50; S, 14.31.

5-(Methylsulfanyl)-2-(morpholin-4-yl)-1-vinyl-1H-pyrrole (4f)

Following the general procedure [using: DMSO (3.5 mL); t-BuOK (1.12 g, 10.0 mmol, 2 equiv), pyrrole 3f (1.40 g, 4.75 mmol, purity 91%): 118–120 °C, 15 min], 1-vinylpyrrole 4f was obtained in a yield of 1.10 g (crude product: 96% purity by ¹H NMR analysis); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1); yield: 0.933 g (88%); yellow prismatic crystals, purity ca. 100% (¹H NMR analysis); mp 57–58 °C.

IR (KBr): 2966 (m), 2916 (m), 2857 (m), 2828 (m), 1637 (s), 1552 (m), 1455 (m), 1407 (m), 1388 (m), 1339 (w), 1313 (m), 1264 (m), 1210 (w), 1158 (w), 1112 (s), 1066 (w), 1032 (sh), 1004 (w), 955 (w), 918 (w), 884 (s), 777 (m), 710 (w), 680 (w), 649 (w), 620 (w), 596 (w), 557 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.14 (dd, ³ J_trans = 16.7 Hz, ³ J_cis = 9.9 Hz, 1 H, NCH=CH₂), 6.29 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.87, 4.92 (dd, ³ J_trans = 16.7 Hz, ³ J_cis = 9.9 Hz, 2 H, NCH=CH ₂), 5.65 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 3.77–3.75 (m, 4 H, CH₂OCH₂), 2.91–2.88 (m, 4 H, CH₂NCH₂), 2.22 (s, 3 H, SCH₃).

¹³C NMR (100 MHz, CDCl₃): δ = 146.0 (C-2), 129.9 (NCH=CH₂), 119.3 (C-5), 116.7 (C-4), 103.4 (C-3), 96.2 (NCH=CH₂), 66.9 (CH₂OCH₂), 52.5 (CH₂NCH₂), 21.2 (SCH₃).

¹⁵N NMR (40 MHz, CDCl₃): δ = –212.1 (N_pyrrole), –328.1 [N(CH₂)₂O(CH₂)₂].

MS (EI, 70 eV): m/z (%) = 225 (15, [M + 1]⁺), 224 (96, [M]⁺), 210 (15), 209 (100), 177 (13), 165 (15), 151 (10), 138 (11), 124 (25), 96 (12), 79 (10).

Anal. Calcd for C₁₁H₁₆N₂OS (224.3): C, 58.90; H, 7.19; N, 12.49; S, 14.29. Found: C, 59.03; H, 7.14; N, 12.40; S, 14.18.

N,N-Diethyl-5-(ethylsulfanyl)-1-vinyl-1H-pyrrol-2-amine (4g)

Following the general procedure [using: DMSO (3 mL); t-BuOK (1.12 g, 10.0 mmol, 2 equiv), pyrrole 3g (1.34 g, 5.0 mmol): 118–120 °C, 15 min], 1-vinylpyrrole 4g was obtained in a yield of 1.02 g [crude product: 91% purity by ¹H NMR analysis; contaminated with unreacted pyrrole 3g (9%)]; isolated by column chromatography (alumina, hexane); yield: 0.90 g (80%); colorless oily liquid, purity ca. 100% (¹H NMR analysis); n _D ²² 1.5367.

IR (neat): 3108 (w), 3078 (w), 3038 (w), 2970 (s), 2925 (s), 2869 (s), 2847 (s), 2829 (s), 1640 (s), 1551 (s), 1453 (s), 1399 (s), 1335 (w), 1279 (s), 1225 (w), 1186 (sh), 1163 (w), 1117 (w), 1087 (m), 1068 (m), 1029 (w), 977 (m), 879 (s), 763 (s), 713 (m), 622 (w), 557 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.14 (dd, ³ J_trans = 16.6 Hz, ³ J_cis = 9.5 Hz, 1 H, NCH=CH₂), 6.33 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.88, 4.83 (dd, ³ J_trans = 16.6 Hz, ³ J_cis = 9.5 Hz, 2 H, NCH=CH ₂), 5.72 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 2.91 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 2.56 (q, ³ J = 7.4 Hz, 2 H, SСН ₂CH₃), 1.13 (t, ³ J = 7.4 Hz, 3 H, SСН₂CH ₃), 0.97 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ = 144.6 (C-2), 130.2 (NCH=CH₂), 118.9 (C-4), 115.9 (C-5), 102.7 (C-3), 99.8 (NCH=CH₂), 48.0 [N(CH₂CH₃)₂], 31.2 (SСН₂CH₃), 14.3 (SСН₂ CH₃), 12.2 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –206.8 (N_pyrrole), –328.5 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 225 (16, [M + 1]⁺), 224 (90, [M]⁺), 196 (18), 195 (100), 168 (11), 167 (11), 166 (40), 151 (16), 140 (37), 137 (23), 134 (10), 96 (19), 79 (20), 70 (12), 59 (14), 56 (11).

Anal. Calcd for C₁₂H₂₀N₂S (224.4): C, 64.24; H, 8.98; N, 12.49; S, 14.29. Found: C, 64.33; H, 8.88; N, 12.35; S, 14.33.

5-(Butylsulfanyl)-N,N-diethyl-1-vinyl-1H-pyrrol-2-amine (4h)

Following the general procedure [using: DMSO (3 mL); t-BuOK (1.12 g, 10.0 mmol, 2 equiv), pyrrole 3h (1.58 g, 5.0 mmol): 118–120 °C, 15 min], 1-vinylpyrrole 4h was obtained in a yield of 1.34 g [crude product: a mixture of pyrroles 4h and 3h in a ratio of ca. 90:10 (¹H NMR analysis)]; isolated by column chromatography (alumina, hexane); yield: 1.15 g (91%); colorless oily liquid, purity ca. 100% (¹H NMR analysis); n _D ²¹ 1.5282.

IR (neat): 3107 (w), 3077 (w), 3038 (w), 2965 (s), 2928 (s), 2868 (s), 2825 (sh), 1640 (s), 1549 (s), 1461 (s), 1399 (s), 1335 (m), 1279 (s), 1247 (w), 1224 (m), 1188 (w), 1163 (m), 1116 (sh), 1087 (sh), 1068 (s), 1027 (w), 1008 (w), 980 (m), 949 (sh), 914 (sh), 878 (s), 786 (sh), 764 (s), 713 (s), 622 (w), 595 (sh), 557 (w), 459 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ = 7.15 (dd, ³ J_trans = 14.6 Hz, ³ J_cis = 9.7 Hz, 1 H, NCH=CH₂), 6.30 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.87, 4.83 (dd, ³ J_trans = 14.6 Hz, ³ J_cis = 9.7 Hz, 2 H, NCH=CH ₂), 5.70 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 2.91 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 2.56 (t, ³ J = 7.3 Hz, 2 H, SСН ₂C₃H₇), 1.50–1.43 (m, 2 H, SСН₂СН ₂C₂H₅), 1.40–1.31 [m, 2 H, S(СН₂)₂СН ₂CH₃], 0.99 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂], 0.85 [t, ³ J = 7.3 Hz, 3 H, S(СН₂)₃CH ₃].

¹³C NMR (100 MHz, CDCl₃): δ = 144.6 (C-2), 130.3 (NCH=CH₂), 118.6 (C-4), 116.4 (C-5), 102.8 (C-3), 99.9 (NCH=CH₂), 48.0 [N(CH₂CH₃)₂], 37.1 (SСН₂C₃H₇), 31.2 (SСН₂ СН₂C₂H₅), 21.8 [S(СН₂)₂ СН₂CH₃], 13.8 [S(СН₂)₃ CH₃], 12.2 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –206.3 (N_pyrrole), –328.7 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 253 (13, [M + 1]⁺), 252 (72, [M]⁺), 196 (19), 195 (100), 151 (11), 140 (29), 137 (17), 124 (17), 112 (11), 96 (11), 79 (12).

Anal. Calcd for C₁₄H₂₄N₂S (252.4): C, 66.62; H, 9.58; N, 11.10; S, 12.70. Found: C, 66.73; H, 9.44; N, 11.15; S, 12.64.

N,N-Diethyl-5-(prop-1-enylsulfanyl)-1-vinyl-1H-pyrrol-2-amine (4i)

Following the general procedure [using: DMSO (3 mL); t-BuOK (1.12 g, 10.0 mmol, 2 equiv), pyrrole 3i (1.42 g, 5.0 mmol): 118–120 °C, 15 min], 1-vinylpyrrole 4i in a mixture with N,N-diethyl-5-(prop-1-enylsulfanyl)-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3i′) (in a ratio of ca. 90:10 by ¹H NMR analysis) was obtained in a yield of 0.76 g (crude product); isolated by column chromatography (alumina, hexane); yield: 0.56 g (47%); a mixture of E/Z-isomers in a ratio of ca. 1:1 (¹H NMR analysis); light-yellow oily liquid; n _D ²² 1.5470. Isolated yield of pyrrole 3i′ was 6% (0.083 g); a mixture of E/Z-isomers in a ratio of ca. 3:2; purity ca. 94%, contaminated with pyrrole 4i (¹H NMR analysis).

4i

IR (neat): 3110 (w), 3079 (w), 3011 (sh), 2970 (s), 2927 (s), 2849 (s), 2826 (sh), 1640 (s), 1550 (s), 1456 (s), 1397 (s), 1332 (w), 1282 (m), 1226 (w), 1163 (w), 1109 (sh), 1071 (m), 1028 (w), 975 (w), 938 (m), 880 (s), 763 (s), 711 (m), 671 (m), 622 (w), 549 (w), 469 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ (E-isomer) = 7.08 (dd, ³ J_trans = 13.8 Hz, ³ J_cis = 9.7 Hz, 1 H, NCH=CH₂), 6.42 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.87 (dq, ³ J_trans = 14.7 Hz, ⁴ J = 1.7 Hz, 1 H, SCH=CHCH₃), 5.80 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 5.77, 4.88 (dd, ³ J_trans = 13.8 Hz, ³ J_cis = 9.7 Hz, 2 H, NCH=CH ₂), 5.38 (dq, ³ J_trans = 14.7 Hz, ³ J = 6.7 Hz, 1 H, SCH=CHCH₃), 2.97 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 1.66 (dd, ³ J = 6.7 Hz, ⁴ J = 1.7 Hz, 3 H, SCH=CHCH ₃), 1.03 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ (E-isomer) = 144.8 (C-2), 129.8 (NCH=CH₂), 125.6 (SCH=CHCH₃), 124.3 (SCH=CHCH₃), 118.7 (C-4), 113.3 (C-5), 103.4 (C-3), 99.9 (NCH=CH₂), 47.9 [N(CH₂CH₃)₂], 18.0 (SCH=CHCH₃), 12.1 [N(CH₂ CH₃)₂].

MS (EI, 70 eV): m/z (%) = 237 (13, [M + 1]⁺), 236 (87, [M]⁺), 207 (11), 203 (27), 180 (14), 166 (15), 165 (56), 164 (14), 163 (18), 147 (11), 138 (11), 137 (16), 136 (14), 135 (17), 134 (100), 133 (16), 132 (10), 123 (10), 119 (12), 118 (10), 110 (23), 108 (15), 107 (11), 106 (24), 105 (43), 99 (11), 97 (12), 96 (16), 93 (12), 80 (17), 79 (58), 72 (10), 59 (12), 54 (12), 53 (10), 52 (14), 39 (12).

¹H NMR (400 MHz, CDCl₃): δ (Z-isomer) = 7.07 (dd, ³ J_trans = 13.8 Hz, ³ J_cis = 9.7 Hz, 1 H, NCH=CH₂), 6.40 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.89 (dq, ³ J_cis = 9.4 Hz, ⁴ J = 1.7 Hz, 1 H, SCH=CHCH₃), 5.77 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 5.81, 4.90 (dd, ³ J_trans = 13.8 Hz, ³ J_cis = 9.7 Hz, 2 H, NCH=CH ₂), 5.60 (dq, ³ J_cis = 9.4 Hz, ³ J = 6.7 Hz, 1 H, SCH=CHCH₃), 2.96 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 1.75 (dd, ³ J = 6.7 Hz, ⁴ J = 1.7 Hz, 3 H, SCH=CHCH ₃), 1.03 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ (Z-isomer) = 144.6 (C-2), 129.7 (NCH=CH₂), 128.4 (SCH=CHCH₃), 122.9 (SCH=CHCH₃), 117.9 (C-4), 114.5 (C-5), 103.2 (C-3), 99.8 (NCH=CH₂), 47.8 [N(CH₂CH₃)₂], 14.0 (SCH=CHCH₃), 12.1 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ (E,Z-isomers) = –207.0 (N_pyrrole), –328.2 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 237 (13, [M + 1]⁺), 236 (70, [M]⁺), 207 (11), 203 (26), 195 (11), 180 (13), 166 (14), 165 (46), 164 (14), 163 (19), 161 (11), 149 (10), 147 (11), 138 (10), 137 (18), 136 (13), 135 (20), 134 (100), 133 (16), 132 (9), 123 (9), 119 (12), 118 (10), 110 (23), 108 (13), 107 (12), 106 (25), 105 (39), 99 (10), 97 (12), 96 (16), 93 (11), 80 (18), 79 (55), 72 (11), 70 (12), 59 (13), 54 (11), 53 (10), 52 (14), 41 (10), 39 (12).

Anal. Calcd for C₁₃H₂₀N₂S (236.4): C, 66.06; H, 8.53; N, 11.85; S, 13.57. Found: C, 66.17; H, 8.42; N, 11.80; S, 13.49.

N,N-Diethyl-5-(prop-1-enylsulfanyl)-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (3i′)

¹H NMR (400 MHz, CDCl₃): δ (E-isomer) = 6.40 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, 1 H, OCH=CH₂), 6.36 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.83 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 5.83 (dq, ³ J_trans = 14.6 Hz, ⁴ J = 1.7 Hz, 1 H, SCH=CHCH₃), 5.31 (dq, ³ J_trans = 14.6 Hz, ³ J = 6.7 Hz, 1 H, SCH=CHCH₃), 4.21 (t, ³ J = 7.1 Hz, 2 H, NCH ₂CH₂O), 4.19, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, ² J_gem = 2.0 Hz, 2 H, OCH=CH ₂), 3.87 (t, ³ J = 7.1 Hz, 2 H, NCH₂CH ₂O), 2.88 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 1.66 (dd, ³ J = 6.7 Hz, ⁴ J = 1.7 Hz, 3 H, SCH=CHCH ₃), 0.98 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ (E-isomer) = 151.6 (OCH=CH₂), 144.5 (C-2), 126.1 (SCH=CHCH₃), 124.2 (SCH=CHCH₃), 117.3 (C-4), 112.8 (C-5), 100.4 (C-3), 86.9 (OCH=CH₂), 67.1 (NCH₂ CH₂O), 49.7 [N(CH₂CH₃)₂], 41.3 (NCH₂CH₂O), 18.1 (SCH=CHCH₃), 12.9 [N(CH₂ CH₃)₂].

MS (EI, 70 eV): m/z (%) = 281 (19, [M + 1]⁺), 280 (100, [M]⁺), 247 (34), 209 (37), 208 (14), 207 (13), 196 (20), 194 (10), 193 (37), 180 (18), 179 (12), 178 (15), 177 (20), 176 (9), 175 (11), 167 (13), 165 (13), 164 (10), 163 (15), 162 (8), 151 (10), 150 (13), 149 (54), 138 (12), 137 (19), 136 (19), 135 (16), 134 (16), 121 (11), 111 (9), 110 (14), 108 (10), 107 (12), 99 (9), 97 (10), 96 (17), 93 (12), 80 (13), 79 (39), 72 (12), 71 (15), 61 (10), 45 (28), 43 (14), 41 (13).

¹H NMR (400 MHz, CDCl₃): δ (Z-isomer) = 6.40 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, 1 H, OCH=CH₂), 6.35 (d, ³ J = 3.8 Hz, 1 H, 4-CH=), 5.82 (dq, ³ J_cis = 9.7 Hz, ⁴ J = 1.7 Hz, 1 H, SCH=CHCH₃), 5.80 (d, ³ J = 3.8 Hz, 1 H, 3-CH=), 5.53 (dq, ³ J_cis = 9.7 Hz, ³ J = 6.7 Hz, 1 H, SCH=CHCH₃), 4.23 (t, ³ J = 7.1 Hz, 2 H, NCH ₂CH₂O), 4.19, 3.98 (dd, ³ J_trans = 14.4 Hz, ³ J_cis = 6.8 Hz, ² J_gem = 2.0 Hz, 2 H, OCH=CH ₂), 3.88 (t, ³ J = 7.1 Hz, 2 H, NCH₂CH ₂O), 2.87 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 1.77 (dd, ³ J = 6.7 Hz, ⁴ J = 1.7 Hz, 3 H, SCH=CHCH ₃), 0.98 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ (Z-isomer) = 151.6 (OCH=CH₂), 144.2 (C-2), 129.0 (SCH=CHCH₃), 123.1 (SCH=CHCH₃), 116.4 (C-4), 114.3 (C-5), 100.4 (C-3), 87.0 (OCH=CH₂), 67.0 (NCH₂ CH₂O), 49.5 [N(CH₂CH₃)₂], 41.3 (NCH₂CH₂O), 14.2 (SCH=CHCH₃), 12.9 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –217.4 (N_pyrrole), –330.7 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 281 (19, [M + 1]⁺), 280 (100, [M]⁺), 247 (40), 209 (48), 208 (16), 207 (16), 196 (22), 194 (11), 193 (41), 180 (22), 179 (11), 178 (17), 177 (28), 176 (11), 175 (14), 167 (15), 165 (16), 164 (12), 163 (17), 162 (10), 151 (11), 150 (14), 149 (57), 138 (12), 137 (21), 136 (19), 135 (20), 134 (18), 121 (13), 111 (12), 110 (16), 108 (12), 107 (14), 99 (12), 97 (11), 96 (19), 93 (15), 80 (15), 79 (48), 72 (11), 71 (17), 61 (10), 45 (36), 43 (16), 41 (15).

5-[(1,3-Dioxolan-2-ylmethyl)sulfanyl]-N,N-diethyl-1-vinyl-1H-pyrrol-2-amine (4l)

(a) Following the general procedure [using: DMSO (2.0 mL); t-BuOK (0.67 g, 6.0 mmol, 3 equiv); pyrrole 3l (0.65 g, 2.0 mmol): 110–112 °C, 10 min], a mixture of pyrroles 3b, 4b, and 4l was obtained in a yield of 0.53 g (crude products); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1); yield: 0.016 g (3%) of 3b, 0.059 g (14%) of 4b, and 0.124 g (22%) of 4l; conversion of pyrrole 3l is 97%.

(b) Following the general procedure [using: DMSO (2.0 mL); t-BuOK (0.45 g, 4.0 mmol, 2 equiv); pyrrole 3l (0.66 g, 2.0 mmol): 108–110 °C, 10 min], pyrrole 4l was obtained in a yield of 0.57 g (crude product); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1, 3:1); yield: 0.156 g (28%); conversion of pyrrole 3l is 78%.

(c) Following the general procedure [using: DMSO (2.0 mL); t-BuOK (0.67 g, 6.0 mmol, 3 equiv); pyrrole 6 (0.65 g, 2.0 mmol): 110–112 °C, 10 min], a mixture of pyrroles 3b, 4b, 3l, and 4l was obtained in a yield of 0.54 g (crude products); isolated by column chromatography (alumina, hexane, hexane–Et₂O, 10:1); yield: 0.022 g (4%) of 3b, 0.053 g (13%) of 4b, 0.014 g (2%) of 3l, and 0.117 g (21%) of 4l.

4l

¹H NMR (400 MHz, CDCl₃): δ = 7.14 (dd, ³ J_trans = 16.2 Hz, ³ J_cis = 9.4 Hz, 1 H, NCH=CH₂), 6.37 (d, ³ J = 3.7 Hz, 1 H, 4-CH=), 5.69 (d, ³ J = 3.7 Hz, 1 H, 3-CH=), 5.89, 4.88 (dd, ³ J_trans = 16.2 Hz, ³ J_cis = 9.4 Hz, 2 H, NCH=CH ₂), 5.01 (t, ³ J = 4.8 Hz, 1 H, OCHO), 3.98–3.87 (m, 4 H, OCH₂CH₂O), 2.92 [q, ³ J = 7.1 Hz, 4 H, N(СН ₂CH₃)₂], 2.74 (d, ³ J = 4.8 Hz, 2 H, SCH₂), 0.97 [t, ³ J = 7.1 Hz, 6 H, N(СН₂CH ₃)₂].

¹³C_Jmod NMR (100 MHz, CDCl₃): δ = 144.7 (C-2), 130.0 (NCH=CH₂), 118.9 (C-4), 115.0 (C-5), 103.2 (NCH=CH₂), 102.8 (OCHO), 99.7 (C-3), 65.1 (ОCH₂CH₂O), 47.7 [N(CH₂CH₃)₂], 40.4 (SCH₂), 12.0 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ = –209.2 (N_pyrrole), –329.8 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 283 (8, [M + 1]⁺), 282 (47, [M]⁺), 196 (13), 195 (100), 166 (24), 165 (18), 163 (14), 140 (17), 137 (17), 125 (36), 124 (14), 96 (11), 79 (18), 45 (20), 43 (15).

Anal. Calcd for C₁₄H₂₂N₂O₂S (282.4): C, 59.54; H, 7.85; N, 9.92; S, 11.35. Found: C, 59.66; H, 7.80; N, 10.01; S, 11.29.

N,N-Diethyl-5-{[2-(2-hydroxyethoxy)ethenyl]sulfanyl}-1-[2-(vinyloxy)ethyl]-1H-pyrrol-2-amine (6)[20]

A mixture of pyrrole 3l (0.65 g, 2.0 mmol), t-BuOK (0.45 g, 4.0 mmol, 2 equiv), and DMSO (1.6 mL) was stirred at r.t. for 1 h. Workup as described above gave a residue (0.60 g, brown liquid) that contained pyrroles 3l and 6 in a ratio of ca. 25:75 (¹H NMR analysis), from which pyrrole 6 was isolated by column chromatography (alumina, hexane–Et₂O, 10:1, 3:1, 1:1, 1:3, Et₂O) in yield of 0.44 g (68%); E/Z ratio = ca. 60:40 (¹H NMR analysis).

IR (neat): 3419 (s), 3111 (w), 3053 (w), 2969 (s), 2932 (s), 2873 (s), 2832 (sh), 1620 (s), 1539 (m), 1449 (s), 1403 (m), 1378 (sh), 1319 (m), 1293 (sh), 1197 (s), 1170 (s), 1109 (sh), 1078 (s), 1012 (sh), 944 (w), 896 (w), 823 (m), 763 (m), 700 (w), 633 (w), 606 (w), 567 (w), 510 (w) cm^–1.

¹H NMR (400 MHz, CDCl₃): δ (E-isomer) = 6.68 (d, ³ J = 12.2 Hz, 1 H, SCH=СНО), 6.41 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.9 Hz, 1 H, OCH=CH₂), 6.31 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 5.77 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 5.35 (d, ³ J = 12.2 Hz, 1 H, SCH=СНО), 4.25 (t, ³ J = 6.8 Hz, 2H, NCH ₂CH₂O), 4.20, 3.99 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.9 Hz, ² J_gem = 2.1 Hz, 2 H, OCH=CH ₂), 3.90 (t, ³ J = 6.8 Hz, 2 H, NCH₂CH ₂O), 3.79−3.74 (m, 4 H, OCH₂CH₂OН), 2.86 [q, ³ J = 7.1 Hz, 4 H, N(CH ₂CH₃)₂], 2.28 (s, 1 Н, ОН), 0.97 [t, ³ J = 7.1 Hz, 6 H, N(CH₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ (E-isomer) = 151.3 (OCH=CH₂), 151.2 (SCH=СНО), 143.8 (C-2), 115.7 (C-4), 115.3 (C-5), 100.0 (C-3), 99.4 (SCH=СНО), 86.8 (OCH=CH₂), 70.8 (ОCH₂ CH₂OН), 66.8 (NCH₂ CH₂O), 61.0 (OCH₂CH₂ОН), 49.2 [N(CH₂CH₃)₂], 41.0 (NCH₂CH₂O), 12.6 [N(CH₂ CH₃)₂].

The ¹H–¹H COSY and ¹H–¹³C HSQC 2D experiments provided additional support for the proposed structure.

¹⁵N NMR (40 MHz, CDCl₃): δ (E-isomer) = –220.1 (N_pyrrole), –332.1 [N(C₂H₅)₂].

¹H NMR (400 MHz, CDCl₃): δ (Z-isomer) = 6.41 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.9 Hz, 1 H, OCH=CH₂), 6.34 (d, ³ J = 3.9 Hz, 1 H, 4-CH=), 6.18 (d, ³ J = 5.3 Hz, 1 H, SCH=СНО), 5.78 (d, ³ J = 3.9 Hz, 1 H, 3-CH=), 4.91 (d, ³ J = 5.3 Hz, 1 H, SCH=СНО), 4.26 (t, ³ J = 6.8 Hz, 2 H, NCH ₂CH₂O), 4.22, 3.99 (dd, ³ J_trans = 14.3 Hz, ³ J_cis = 6.9 Hz, ² J_gem = 2.1 Hz, 2 H, OCH=CH ₂), 3.80−3.73 (m, 2 H, OCH₂CH ₂OН), 3.88 (t, ³ J = 6.8 Hz, 2 H, NCH₂CH ₂O), 3.79–3.74 (m, 2 H, OCH ₂CH₂OН), 2.86 [q, ³ J = 7.1 Hz, 4 H, N(CH ₂CH₃)₂], 2.58 (s, 1 Н, ОН), 0.97 [t, ³ J = 7.1 Hz, 6 H, N(CH₂CH ₃)₂].

¹³C NMR (100 MHz, CDCl₃): δ (Z-isomer) = 151.0 (OCH=CH₂), 144.7 (SCH=СНО), 143.9 (C-2), 116.0 (C-4), 114.2 (C-5), 100.0 (C-3), 103.1 (SCH=СНО), 86.9 (OCH=CH₂), 74.2 (ОCH₂ CH₂OН), 66.7 (NCH₂ CH₂O), 62.0 (OCH₂CH₂ОН), 49.2 [N(CH₂CH₃)₂], 41.0 (NCH₂CH₂O), 12.6 [N(CH₂ CH₃)₂].

¹⁵N NMR (40 MHz, CDCl₃): δ (Z-isomer) = –219.7 (N_pyrrole), –332.1 [N(C₂H₅)₂].

MS (EI, 70 eV): m/z (%) = 327 (20, [M + 1]⁺), 326 (100, [M]⁺), 293 (40), 281 (20), 255 (43), 209 (13), 207 (19), 196 (10), 193 (32), 183 (25), 181 (13), 179 (11), 177 (14), 168 (11), 167 (18), 166 (18), 165 (11), 163 (12), 154 (13), 153 (12), 151 (19), 149 (41), 139 (13), 138 (14), 137 (19), 136 (14), 135 (19), 126 (12), 121 (15), 110 (21), 108 (12), 107 (18), 96 (15), 80 (16), 79 (47), 73 (25), 71 (15), 45 (77), 43 (23).

Anal. Calcd for C₁₆H₂₆N₂O₃S (326.5): C, 58.87; H, 8.03; N, 8.58; S, 9.82. Found: C, 58.99; H, 8.10; N, 8.51; S, 9.74.

Conflict of Interest

The authors declare no conflict of interest.

Acknowledgment

The reported study was performed, using the equipment of Baikal Analytical Centre for collective use Siberian Branch of the Russian Academy of Sciences.

• References

• 1a Black DStC. 1H-Pyrroles. In Science of Synthesis: Houben-Weyl Methods of Molecular Transformations, Vol. 9. Maas G. Thieme; Stuttgart: 2001: 441
  Search in Google Scholar
• 1b Joshi SD, More UA, Kulkarni VH, Aminabhavi TM. Curr. Org. Chem. 2013; 17: 2279
  CrossrefSearch in Google Scholar
• 1c Estévez V, Villacampa M, Menéndez JC. Chem. Soc. Rev. 2014; 43: 4633
  CrossrefPubMedSearch in Google Scholar
• 1d Bellur E, Langer P. Tetrahedron Lett. 2006; 47: 2151
  CrossrefSearch in Google Scholar
• 1e Demir AS, Emrullahoglu M, Ardahan G. Tetrahedron 2007; 63: 461
  CrossrefSearch in Google Scholar
• 1f Attanasi OA, Berretta S, De Crescentini L, Favi G, Giorgi G, Mantellini F, Nicolini S. Adv. Synth. Catal. 2011; 353: 595
  CrossrefSearch in Google Scholar
• 1g Reekie TA, Donckele EJ, Manenti G, Püntener S, Trapp N, Diederich FA. Org. Lett. 2016; 18: 2252
  CrossrefPubMedSearch in Google Scholar
• 1h Guchhait SK, Sisodiya S, Saini M, Shah YV, Kumar G, Daniel DP, Hura N, Chaudhary V. J. Org. Chem. 2018; 83: 5807
  CrossrefPubMedSearch in Google Scholar
• 2a Baxendale IR, Buckle CD, Ley SV, Tamborini L. Synthesis 2009; 1485
• 2b Marth G, Anderson RJ, Thompson BG, Ashton M, Groundwater PW. Tetrahedron 2010; 66: 6113
  CrossrefSearch in Google Scholar
• 2c Fitzgerald MA, Soltani O, Wei C, Skliar D, Zheng B, Li J, Albrecht J, Schmidt M, Mahoney M, Fox RJ, Tran K, Zhu K, Eastgate MD. J. Org. Chem. 2015; 80: 6001
  CrossrefPubMedSearch in Google Scholar
• 3a Khajuria R, Dham S, Kapoor KK. RSC Adv. 2016; 6: 37039
  CrossrefSearch in Google Scholar
• 3b Gholap SS. Eur. J. Med. Chem. 2016; 110: 13
  CrossrefPubMedSearch in Google Scholar
• 3c Brachet E, Belmont P. J. Org. Chem. 2015; 80: 7519
  CrossrefPubMedSearch in Google Scholar
• 3d Renneberg D, Dervan PB. J. Am. Chem. Soc. 2003; 125: 5707
  CrossrefPubMedSearch in Google Scholar
• 3e Lee JE, Yoon KJ, Lee YS. Bioorg. Med. Chem. Lett. 2003; 13: 4331
  CrossrefPubMedSearch in Google Scholar
• 3f Hilmy KM. H, Soliman DH, Shahin EB. A, Alhameed RA. Life Sci. J. 2012; 9: 736
  Search in Google Scholar
• 4a Huffman JW. Cannabimimetic Indoles, Pyrroles, and Indenes: Structure–Activity Relationships and Receptor Interactions. In The Cannabinoid Receptors, The Receptors. Reggio PH. Humana Press; a part of Springer Science + Business Media, LLC: 2009: 49
  CrossrefSearch in Google Scholar
• 4b Huffman JW, Padgett LW. Curr. Med. Chem. 2005; 12: 1395
  CrossrefPubMedSearch in Google Scholar
• 4c Baumann M, Baxendale IR, Ley SV, Ni N. Beilstein J. Org. Chem. 2011; 7: 442
  CrossrefPubMedSearch in Google Scholar
• 4d Bhardwaj V, Gumber D, Abbot V, Dhiman S, Sharma P. RSC Adv. 2015; 5: 15233
  CrossrefSearch in Google Scholar
• 4e Kidwai M, Venkataramanan R, Mohan R, Sapra P. Curr. Med. Chem. 2002; 9: 1209
  CrossrefPubMedSearch in Google Scholar
• 4f Pandey PS, Rao TS. Bioorg. Med. Chem. Lett. 2004; 14: 129
  CrossrefPubMedSearch in Google Scholar
• 5a Brustolin F, Castelvetro V, Ciardelli F, Ruggeri G, Colligiani A. J. Polym. Sci., Part A: Polym. Chem. 2001; 39: 253
  CrossrefSearch in Google Scholar
• 5b Facchetti A, Abbotto A, Beverina L, van der Boom ME, Dutta P, Evmenenko G, Marks TJ, Pagani GA. Chem. Mater. 2002; 14: 4996
  CrossrefSearch in Google Scholar
• 5c Gallopini E. Coord. Chem. Rev. 2004; 248: 1283
  CrossrefSearch in Google Scholar
• 6a Jones RA, Bean GP. Hydroxy- and Aminopyrroles and Related Compounds. In The Chemistry of Pyrroles: Organic Chemistry: A Series of Monographs, Vol. 34. Blomquist AT, Wasserman HH. 1977: 379
  Search in Google Scholar
• 6b Cirrincione G, Almerico AM, Aiello E, Dattolo G. Pyrroles, Part 2: The Synthesis, Reactivity, and Physical Properties of Substituted Pyrroles. In The Chemistry of Heterocyclic Compounds, Vol. 48. Taylor EC. Wiley; New York: 1992: 299
  CrossrefSearch in Google Scholar
• 6c Chen N, Lu Y, Gadamasetti K, Hurt CR, Norman MH, Fotsch C. J. Org. Chem. 2000; 65: 2603
  CrossrefPubMedSearch in Google Scholar
• 6d Mohamed MS, El-Domany RA, El-Hameed RH. Acta Pharm. 2009; 59: 145
  CrossrefPubMedSearch in Google Scholar
• 6e Jalani HB, Pandya AN, Baraiya AB, Kaila JC, Pandya DH, Sharma JA, Sudarsanam V, Vasu KK. Tetrahedron Lett. 2011; 52: 6331
  CrossrefSearch in Google Scholar
• 6f Frolova LV, Evdokimov NM, Hayden K, Malik I, Rogelj S, Kornienko A, Magedov IV. Org. Lett. 2011; 13: 1118
  CrossrefPubMedSearch in Google Scholar
• 6g Montalbano A, Parrino B, Diana P, Barraja P, Carbone A, Spanò V, Cirrincione G. Tetrahedron 2013; 69: 2550
  CrossrefSearch in Google Scholar
• 6h Yu W, Chen W, Liu S, Shao J, Shao Z, Lin H, Yu Y. Tetrahedron 2013; 69: 1953
  CrossrefSearch in Google Scholar
• 6i Xiao X.-Y, Zhou A.-H, Shu C, Pan F, Li T, Ye L.-W. Chem. Asian J. 2015; 10: 1854
  CrossrefPubMedSearch in Google Scholar
• 6j Shao J, Ke D, Shu K, Chen E, Yu Y, Chen W. Synlett 2018; 29: 922
  Thieme ConnectSearch in Google Scholar
• 6k Liu X, Nie Z, Shao J, Chen W, Yu Y. New J. Chem. 2018; 42: 2368
  CrossrefSearch in Google Scholar
• 6l Aksu K, Özgeriş B, Tümer F. Org. Commun. 2019; 12: 38
  CrossrefSearch in Google Scholar
• 6m Galenko EE, Linnik SA, Khoroshilova OV, Novikov MS, Khlebnikov AF. J. Org. Chem. 2019; 84: 11275
  CrossrefPubMedSearch in Google Scholar
• 7a Rapoport H, Willson CD. J. Am. Chem. Soc. 1962; 84: 630
  CrossrefSearch in Google Scholar
• 7b Karpfen A, Schuster P, Berner H. J. Org. Chem. 1979; 44: 37
  CrossrefSearch in Google Scholar
• 7c Merz A, Kronberger J, Dunsch L, Neudeck A, Petr A, Parkanyi L. Angew. Chem. Int. Ed. 1999; 38: 1442
  CrossrefPubMedSearch in Google Scholar
• 7d Boger DL, Hong J. J. Am. Chem. Soc. 2001; 123: 8515
  CrossrefPubMedSearch in Google Scholar
• 7e Gao G.-Y, Colvin AJ, Chen Y, Zhang XP. Org. Lett. 2003; 5: 3261
  CrossrefPubMedSearch in Google Scholar
• 7f Merz A, Anikin S, Lieser B, Heinze J, John H. Chem. Eur. J. 2003; 9: 449
  CrossrefPubMedSearch in Google Scholar
• 7g Fürstner A. Angew. Chem. Int. Ed. 2003; 42: 3582
  CrossrefPubMedSearch in Google Scholar
• 7h Bonauer C, Zabel M, König B. Org. Lett. 2004; 6: 1349
  CrossrefPubMedSearch in Google Scholar
• 7i Kruppa M, Bonauer C, Michlov V, Knig B. J. Org. Chem. 2005; 70: 5305
  CrossrefPubMedSearch in Google Scholar
• 7j Hill L, Imam SH, McNab H, O’Neill WJ. Synthesis 2009; 2535
• 7k Rana A, Panda PK. Tetrahedron Lett. 2011; 52: 2697
  CrossrefSearch in Google Scholar
• 7l Sun S.-q, Cheng J, Wang Y.-j, Zhu C.-j, Xu W, Liu X.-x. Anhui Nongye Kexue 2012; 40: 12633
  Search in Google Scholar
• 7m Zahng M, Fang X, Neumann H, Beller M. J. Am. Chem. Soc. 2013; 135: 11384
  CrossrefPubMedSearch in Google Scholar
• 7n Danevčič T, Borić Vezjak M, Zorec M, Stopar D. PLoS One 2016; 11: e0162412
  CrossrefPubMedSearch in Google Scholar
• 8a Berlin A, Pagani GA, Schiavon G, Zotti G. J. Chem. Soc., Perkin Trans. 2 1990; 699
  Crossref
• 8b Boiadjiev SE, Lightner DA. J. Org. Chem. 1998; 63: 6220
  CrossrefPubMedSearch in Google Scholar
• 8c Alemán C, Domingo VM, Julia L. J. Phys. Chem. A 2001; 105: 5266
  CrossrefSearch in Google Scholar
• 8d Domingo VM, Brillas E, Torrelles X, Rius J, Julia L. J. Org. Chem. 2001; 66: 8236
  CrossrefPubMedSearch in Google Scholar
• 8e Rosa A, Ricciardi G, Baerends EJ, Zimin M, Rodgers MA. J, Matsumoto S, Ono N. Inorg. Chem. 2005; 44: 6609
  CrossrefPubMedSearch in Google Scholar
• 8f Li H, Lambert C, Stahl R. Macromolecules 2006; 39: 2049
  CrossrefSearch in Google Scholar
• 8g Thamyongkit P, Bhise AD, Taniguchi M, Lindsey JS. J. Org. Chem. 2006; 71: 903
  CrossrefPubMedSearch in Google Scholar
• 8h Loudet A, Burgess K. Chem. Rev. 2007; 107: 4891
  CrossrefPubMedSearch in Google Scholar
• 8i Peng L, Zhang X, Ma J, Zhong Z, Wang J. Org. Lett. 2007; 9: 1445
  CrossrefPubMedSearch in Google Scholar
• 8j Misra NC, Panda K, Ila H, Junjappa H. J. Org. Chem. 2007; 72: 1246
  CrossrefPubMedSearch in Google Scholar
• 8k Yin G, Wang Z, Chen A, Gao M, Wu A, Pan Y. J. Org. Chem. 2008; 73: 3377
  CrossrefPubMedSearch in Google Scholar
• 8l Gillis HM, Greene L, Thompson A. Synlett 2009; 112
• 8m Heinze J, Frontana-Uribe BA, Ludwigs S. Chem. Rev. 2010; 110: 4724
  CrossrefPubMedSearch in Google Scholar
• 8n Belviso S, Santoro E, Lelj F, Casarini D, Villani C, Franzini R, Superchi S. Eur. J. Org. Chem. 2018; 4029
  Crossref
• 8o Xu W, Hei Y.-Y, Song J.-L, Zhan X.-C, Zhang X.-G, Deng C.-L. Synthesis 2019; 51: 545
  Thieme ConnectSearch in Google Scholar
• 9a Fegley MF, Bortnick NM, McKeever LH. J. Am. Chem. Soc. 1957; 79: 4144
  CrossrefSearch in Google Scholar
• 9b Kalaycioglu E, Toppare L, Yagci Y. Synth. Met. 2000; 108: 1
  CrossrefSearch in Google Scholar
• 9c Brandsma L, Nedolya NA, Tolmachev SV. Chem. Heterocycl. Compd. 2002; 38: 54
  CrossrefSearch in Google Scholar
• 9d Nedolya NA, Brandsma L, Tolmachev SV. Russ. J. Org. Chem. 2002; 38: 907
  CrossrefSearch in Google Scholar
• 9e Nedolya NA, Brandsma L, Shlyakhtina NI. Russ. J. Org. Chem. 2002; 38: 1070
  CrossrefSearch in Google Scholar
• 9f Uyar T, Toppare L, Hacaloğlu J. J. Anal. Appl. Pyrolysis 2003; 68–69: 15
  CrossrefSearch in Google Scholar
• 9g Sadykov EK, Lobanova NA, Stankevich VK. Synthesis 2015; 47: 672
  Thieme ConnectSearch in Google Scholar
• 9h Sadykov EK, Lobanova NA, Stankevich VK. Russ. J. Org. Chem. 2016; 52: 533
  CrossrefSearch in Google Scholar
• 10a Trofimov BA. Vinylpyrroles, Chapter 2: Pyrroles. In The Chemistry of the Heterocyclic Compounds, Vol. 48. Jones RA. Wiley; New York: 1992: 131
  CrossrefSearch in Google Scholar
• 10b Trofimov BA, Mikhaleva AI, Morozova LV. Russ. Chem. Rev. 1985; 54: 609
  CrossrefSearch in Google Scholar
• 10c Settambolo R, Caiazzo A, Lazzaroni R. J. Organomet. Chem. 1996; 506: 337
  CrossrefSearch in Google Scholar
• 10d Caiazzo A, Settambolo R, Uccello-Barretta G, Lazzaroni R. J. Organomet. Chem. 1997; 548: 279
  CrossrefSearch in Google Scholar
• 10e DuBois CJ. Jr, McCarley RL. J. Electroanal. Chem. 1998; 454: 99
  CrossrefSearch in Google Scholar
• 10f Varlamov AV, Borisova TN, Voskressensky LG, Brook AA, Chernyshev AI. ARKIVOC 2000; : 147
  Crossref
• 10g Pinho e Melo TM. V. D, Soares MI. L, Rocha Gonsalves AM. d'A, Paixão JA, Beja AM, Silva MR. J. Org. Chem. 2005; 70: 6629
  CrossrefPubMedSearch in Google Scholar
• 10h Trofimov BA, Markova MV, Morozova LV, Shmidt EYu, Senotrusova EYu, Myachina GF, Myachin YuA, Vakul’skaya TI, Mikhaleva AI. Polym. Sci. Ser. B 2007; 49: 292
  CrossrefSearch in Google Scholar
• 10i Morozova LV, Tatarinova IV, Markova MV, Vasil’tsov AM, Ivanov AV, Vakul’skaya TI, Mikhaleva AI, Trofimov BA. Russ. Chem. Bull. Int. Ed. 2007; 56: 2209
  CrossrefSearch in Google Scholar
• 10j Trofimov BA, Mikhaleva AI, Shmidt EYu, Sobenina LN. Pyrroles and N-Vinylpyrroles from Ketones and Acetylenes: Recent Studies . In Advances in Heterocyclic Chemistry, Vol. 99. Katritzky AR. Academic Press; New York: 2010: 209
  Search in Google Scholar
• 10k Trofimov BA, Markova MV, MorozovaL V, Mikhaleva AI, Shmidt EYu, Zorina NV, Hyun SH. Polym. Sci. Ser. B 2010; 52: 193
  CrossrefSearch in Google Scholar
• 10l Trofimov BA, Markova MV, Morozova LV, Mikhaleva AI, Sobenina LN, Petrova OV, Vakul’skaya TI, Myachina GF, Petrushenko KB. Synth. Met. 2010; 160: 1539
  CrossrefSearch in Google Scholar
• 10m Luo J, Qin J, Kang H, Ye C. Chem. Mater. 2001; 13: 927
  CrossrefSearch in Google Scholar
• 10n Afonin AV, Pavlov DV, Albanov AI, Tarasova OA, Nedolya NA. Magn. Reson. Chem. 2013; 51: 414
  CrossrefPubMedSearch in Google Scholar
• 10o Molchanov AP, Savinkov RS, Stepakov AV, Starova GL, Kostikov RR, Barnakova VS, Ivanov AV. Synthesis 2014; 46: 771
  Thieme ConnectSearch in Google Scholar
• 11a Tarasova OA, Nedolya NA, Vvedensky VYu, Brandsma L, Trofimov BA. Tetrahedron Lett. 1997; 38: 7241
  CrossrefSearch in Google Scholar
• 11b Nedolya NA, Brandsma L, Tarasova OA, Verkruijsse HD, Trofimov BA. Tetrahedron Lett. 1998; 39: 2409
  CrossrefSearch in Google Scholar
• 11c Brandsma L, Nedolya NA, Trofimov BA. Eur. J. Org. Chem. 1999; 2663
  Crossref
• 11d Brandsma L, Nedolya NA, Tarasova OA, Trofimov BA. Chem. Heterocycl. Compd. 2000; 36: 1241
  CrossrefSearch in Google Scholar
• 11e Nedolya NA, Brandsma L, Tolmachev SV. Chem. Heterocycl. Compd. 2002; 38: 745
  CrossrefSearch in Google Scholar
• 11f Brandsma L, Nedolya NA. Synthesis 2004; 735
  Thieme Connect
• 11g Nedolya NA, Brandsma L. Russ. J. Org. Chem. 2006; 42: 607
  CrossrefSearch in Google Scholar
• 11h Nedolya NA, Brandsma L, Tarasova OA, Albanov AI, Trofimov BA. Russ. J. Org. Chem. 2011; 47: 659
  CrossrefSearch in Google Scholar
• 11i Nedolya NA, Tarasova OA, Albanov AI, Trofimov BA. Synthesis 2016; 48: 4278
  Thieme ConnectSearch in Google Scholar
• 11j Tarasova OA, Nedolya NA, Albanov AI, Trofimov BA. Eur. J. Org. Chem. 2018; 5961
  Crossref
• 11k Tarasova OA, Nedolya NA, Albanov AI, Trofimov BA. Synthesis 2019; 51: 3697
  Thieme ConnectSearch in Google Scholar
• 11l Tarasova OA, Nedolya NA, Albanov AI, Trofimov BA. ChemistrySelect 2020; 5: 5726
  CrossrefSearch in Google Scholar
• 11m Tarasova OA, Nedolya NA, Albanov AI, Bagryanskaya IYu, Trofimov BA. J. Organomet. Chem. 2021; 933: 121651
  CrossrefSearch in Google Scholar
• 12a Reppe W. Liebigs Ann. Chem. 1956; 601: 81
  CrossrefSearch in Google Scholar
• 12b Tzalis D, Koradin C, Knochel P. Tetrahedron Lett. 1999; 40: 6193
  CrossrefSearch in Google Scholar
• 12c Trofimov BA, Sobenina LN, Mikhaleva AI, Ushakov IA, Vakul’skaya TI, Stepanova ZV, Toryashinova D.-SD, Mal’kina AG, Elokhina VN. Synthesis 2003; 1272
• 12d Verma AK, Joshi M, Singh VP. Org. Lett. 2011; 13: 1630
  CrossrefPubMedSearch in Google Scholar
• 12e Patel M, Saunthwal RK, Verma AK. Acc. Chem. Res. 2017; 50: 240
  CrossrefPubMedSearch in Google Scholar
• 12f Trofimov BA, Tarasova OA, Shemetova MA, Afonin AV, Klyba LV, Baikalova LV, Mikhaleva AI. Russ. J. Org. Chem. 2003; 39: 408
  CrossrefSearch in Google Scholar
• 13a Gonzales C, Greenhouse R, Tallabs R. Can. J. Chem. 1983; 61: 1697
  CrossrefSearch in Google Scholar
• 13b Settambolo R, Mariani M, Caiazzo A. J. Org. Chem. 1998; 63: 10022
  CrossrefSearch in Google Scholar
• 13c Abele E, Dzenitis O, Rubina R, Lukevics E. Chem. Heterocycl. Compd. 2002; 38: 682
  CrossrefSearch in Google Scholar
• 13d Di Santo R, Tafi A, Costi R, Botta M, Artico M, Corelli F, Forte M, Caporuscio F, Angiolella L, Palamara AT. J. Med. Chem. 2005; 48: 5140
  CrossrefPubMedSearch in Google Scholar
• 13e Wang W, Yu D, Tian F. Synth. Met. 2008; 158: 717
  CrossrefSearch in Google Scholar
• 13f Petrova OV, Markova MV, Sobenina LN, Morozova LV, Mikhaleva AI, Hyun SH, Trofimov BA. Russ. Chem. Bull. 2009; 58: 115
  CrossrefSearch in Google Scholar
• 13g Lan T, Chen X, Liu Z, Mao Z. J. Heterocycl. Chem. 2013; 50: 1094
  CrossrefSearch in Google Scholar
• 14a Lebedev AY, Izmer VV, Kazyul’kin DN, Beletskaya IP, Voskoboynikov AZ. Org. Lett. 2002; 4: 623
  CrossrefPubMedSearch in Google Scholar
• 14b Taillefer M, Ouali A, Renard B, Spindler J.-F. Chem. Eur. J. 2006; 12: 5301
  CrossrefPubMedSearch in Google Scholar
• 14c Liao Q, Wang Y, Zhang L, Xi C. J. Org. Chem. 2009; 74: 6371
  CrossrefPubMedSearch in Google Scholar
• 15 Movassaghi M, Ondrus AE. J. Org. Chem. 2005; 70: 8638
  CrossrefPubMedSearch in Google Scholar
• 16 Kukharev BF, Stankevich VK, Kukhareva VA. Russ. J. Org. Chem. 2011; 47: 614
  CrossrefSearch in Google Scholar
• 17 Nedolya NA, Tarasova OA, Albanov AI, Trofimov BA. Tetrahedron Lett. 2010; 51: 5316
  CrossrefSearch in Google Scholar
• 18 Albano VG, Gualandi A, Monari M, Savoia D. J. Org. Chem. 2008; 73: 8376
  CrossrefPubMedSearch in Google Scholar
• 19a Mikhaleva AI, Shmidt EYu, Ivanov AV, Vasil’tsov AM, Senotrusova EYu, Protsuk NI. Russ. J. Org. Chem. 2007; 43: 228
  CrossrefSearch in Google Scholar
• 19b Trofimov BA, Mikhaleva AI, Shmidt EYu, Sobenina LN. Adv. Heterocycl. Chem. 2010; 99: 209
  CrossrefSearch in Google Scholar
• 19c Vasil’tsov AM, Ivanov AV, Mikhaleva AI, Trofimov BA. Tetrahedron Lett. 2010; 51: 1690
  CrossrefSearch in Google Scholar
• 19d Trofimov BA, Mikhaleva AI, Shmidt EYu, Sobenina LN. Chemistry of Pyrroles . CRC Press-Taylor & Fransis Group; Boca-Raton: 2014
  CrossrefSearch in Google Scholar
• 20 Nedolya NA, Tarasova OA, Аlbanov АI, Trofimov B. А. Russ. J. Org. Chem. 2021; 57: 486
  CrossrefSearch in Google Scholar
• 21a Trofimov BA, Parshina LN, Lavrov VI, Oparina LA. Russ. Chem. Bull. 1984; 33: 1532
  CrossrefSearch in Google Scholar
• 21b Trofimov BA, Oparina LA, Parshina LN, Lavrov VI, Grigorenko VI, Zhumabekov MK. Zh. Org. Khim. 1986; 22: 1583
  Search in Google Scholar
• 22a Wu X.-F, Natte K. Adv. Synth. Catal. 2016; 358: 336
  CrossrefPubMedSearch in Google Scholar
• 22b Tashrifi Z, Khanaposhtani MM, Larijani B, Mahdavi M. Adv. Synth. Catal. 2020; 362: 65
  CrossrefSearch in Google Scholar
• 23a Brandsma L. Best Synthetic Methods: Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques. Elsevier; Amsterdam: 2004
  Search in Google Scholar
• 23b Verkruijsse HD, Bos HJ. T, de Noten LJ, Brandsma L. Recl. Trav. Chim. Pays-Bas 1981; 100: 244
  CrossrefSearch in Google Scholar
• 24a Trofimov BA, Nedolya NA, Gerasimova VV, Voronkov MG. Sulfur Lett. 1988; 8: 73
  Search in Google Scholar
• 24b Trofimov BA, Nedolya NA, Papsheva NP, Gerasimova VV, Voronkov MG. Zh. Org. Khim. 1988; 24: 1771 ; Chem. Abstr. 1989, 110, 74812c
  Search in Google Scholar

Corresponding Authors

Publication History

Received: 02 March 2022

Accepted after revision: 07 April 2022

Accepted Manuscript online:
07 April 2022

Article published online:
14 June 2022

© 2022. Thieme. All rights reserved

Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany

• References

• 1a Black DStC. 1H-Pyrroles. In Science of Synthesis: Houben-Weyl Methods of Molecular Transformations, Vol. 9. Maas G. Thieme; Stuttgart: 2001: 441
  Search in Google Scholar
• 1b Joshi SD, More UA, Kulkarni VH, Aminabhavi TM. Curr. Org. Chem. 2013; 17: 2279
  CrossrefSearch in Google Scholar
• 1c Estévez V, Villacampa M, Menéndez JC. Chem. Soc. Rev. 2014; 43: 4633
  CrossrefPubMedSearch in Google Scholar
• 1d Bellur E, Langer P. Tetrahedron Lett. 2006; 47: 2151
  CrossrefSearch in Google Scholar
• 1e Demir AS, Emrullahoglu M, Ardahan G. Tetrahedron 2007; 63: 461
  CrossrefSearch in Google Scholar
• 1f Attanasi OA, Berretta S, De Crescentini L, Favi G, Giorgi G, Mantellini F, Nicolini S. Adv. Synth. Catal. 2011; 353: 595
  CrossrefSearch in Google Scholar
• 1g Reekie TA, Donckele EJ, Manenti G, Püntener S, Trapp N, Diederich FA. Org. Lett. 2016; 18: 2252
  CrossrefPubMedSearch in Google Scholar
• 1h Guchhait SK, Sisodiya S, Saini M, Shah YV, Kumar G, Daniel DP, Hura N, Chaudhary V. J. Org. Chem. 2018; 83: 5807
  CrossrefPubMedSearch in Google Scholar
• 2a Baxendale IR, Buckle CD, Ley SV, Tamborini L. Synthesis 2009; 1485
• 2b Marth G, Anderson RJ, Thompson BG, Ashton M, Groundwater PW. Tetrahedron 2010; 66: 6113
  CrossrefSearch in Google Scholar
• 2c Fitzgerald MA, Soltani O, Wei C, Skliar D, Zheng B, Li J, Albrecht J, Schmidt M, Mahoney M, Fox RJ, Tran K, Zhu K, Eastgate MD. J. Org. Chem. 2015; 80: 6001
  CrossrefPubMedSearch in Google Scholar
• 3a Khajuria R, Dham S, Kapoor KK. RSC Adv. 2016; 6: 37039
  CrossrefSearch in Google Scholar
• 3b Gholap SS. Eur. J. Med. Chem. 2016; 110: 13
  CrossrefPubMedSearch in Google Scholar
• 3c Brachet E, Belmont P. J. Org. Chem. 2015; 80: 7519
  CrossrefPubMedSearch in Google Scholar
• 3d Renneberg D, Dervan PB. J. Am. Chem. Soc. 2003; 125: 5707
  CrossrefPubMedSearch in Google Scholar
• 3e Lee JE, Yoon KJ, Lee YS. Bioorg. Med. Chem. Lett. 2003; 13: 4331
  CrossrefPubMedSearch in Google Scholar
• 3f Hilmy KM. H, Soliman DH, Shahin EB. A, Alhameed RA. Life Sci. J. 2012; 9: 736
  Search in Google Scholar
• 4a Huffman JW. Cannabimimetic Indoles, Pyrroles, and Indenes: Structure–Activity Relationships and Receptor Interactions. In The Cannabinoid Receptors, The Receptors. Reggio PH. Humana Press; a part of Springer Science + Business Media, LLC: 2009: 49
  CrossrefSearch in Google Scholar
• 4b Huffman JW, Padgett LW. Curr. Med. Chem. 2005; 12: 1395
  CrossrefPubMedSearch in Google Scholar
• 4c Baumann M, Baxendale IR, Ley SV, Ni N. Beilstein J. Org. Chem. 2011; 7: 442
  CrossrefPubMedSearch in Google Scholar
• 4d Bhardwaj V, Gumber D, Abbot V, Dhiman S, Sharma P. RSC Adv. 2015; 5: 15233
  CrossrefSearch in Google Scholar
• 4e Kidwai M, Venkataramanan R, Mohan R, Sapra P. Curr. Med. Chem. 2002; 9: 1209
  CrossrefPubMedSearch in Google Scholar
• 4f Pandey PS, Rao TS. Bioorg. Med. Chem. Lett. 2004; 14: 129
  CrossrefPubMedSearch in Google Scholar
• 5a Brustolin F, Castelvetro V, Ciardelli F, Ruggeri G, Colligiani A. J. Polym. Sci., Part A: Polym. Chem. 2001; 39: 253
  CrossrefSearch in Google Scholar
• 5b Facchetti A, Abbotto A, Beverina L, van der Boom ME, Dutta P, Evmenenko G, Marks TJ, Pagani GA. Chem. Mater. 2002; 14: 4996
  CrossrefSearch in Google Scholar
• 5c Gallopini E. Coord. Chem. Rev. 2004; 248: 1283
  CrossrefSearch in Google Scholar
• 6a Jones RA, Bean GP. Hydroxy- and Aminopyrroles and Related Compounds. In The Chemistry of Pyrroles: Organic Chemistry: A Series of Monographs, Vol. 34. Blomquist AT, Wasserman HH. 1977: 379
  Search in Google Scholar
• 6b Cirrincione G, Almerico AM, Aiello E, Dattolo G. Pyrroles, Part 2: The Synthesis, Reactivity, and Physical Properties of Substituted Pyrroles. In The Chemistry of Heterocyclic Compounds, Vol. 48. Taylor EC. Wiley; New York: 1992: 299
  CrossrefSearch in Google Scholar
• 6c Chen N, Lu Y, Gadamasetti K, Hurt CR, Norman MH, Fotsch C. J. Org. Chem. 2000; 65: 2603
  CrossrefPubMedSearch in Google Scholar
• 6d Mohamed MS, El-Domany RA, El-Hameed RH. Acta Pharm. 2009; 59: 145
  CrossrefPubMedSearch in Google Scholar
• 6e Jalani HB, Pandya AN, Baraiya AB, Kaila JC, Pandya DH, Sharma JA, Sudarsanam V, Vasu KK. Tetrahedron Lett. 2011; 52: 6331
  CrossrefSearch in Google Scholar
• 6f Frolova LV, Evdokimov NM, Hayden K, Malik I, Rogelj S, Kornienko A, Magedov IV. Org. Lett. 2011; 13: 1118
  CrossrefPubMedSearch in Google Scholar
• 6g Montalbano A, Parrino B, Diana P, Barraja P, Carbone A, Spanò V, Cirrincione G. Tetrahedron 2013; 69: 2550
  CrossrefSearch in Google Scholar
• 6h Yu W, Chen W, Liu S, Shao J, Shao Z, Lin H, Yu Y. Tetrahedron 2013; 69: 1953
  CrossrefSearch in Google Scholar
• 6i Xiao X.-Y, Zhou A.-H, Shu C, Pan F, Li T, Ye L.-W. Chem. Asian J. 2015; 10: 1854
  CrossrefPubMedSearch in Google Scholar
• 6j Shao J, Ke D, Shu K, Chen E, Yu Y, Chen W. Synlett 2018; 29: 922
  Thieme ConnectSearch in Google Scholar
• 6k Liu X, Nie Z, Shao J, Chen W, Yu Y. New J. Chem. 2018; 42: 2368
  CrossrefSearch in Google Scholar
• 6l Aksu K, Özgeriş B, Tümer F. Org. Commun. 2019; 12: 38
  CrossrefSearch in Google Scholar
• 6m Galenko EE, Linnik SA, Khoroshilova OV, Novikov MS, Khlebnikov AF. J. Org. Chem. 2019; 84: 11275
  CrossrefPubMedSearch in Google Scholar
• 7a Rapoport H, Willson CD. J. Am. Chem. Soc. 1962; 84: 630
  CrossrefSearch in Google Scholar
• 7b Karpfen A, Schuster P, Berner H. J. Org. Chem. 1979; 44: 37
  CrossrefSearch in Google Scholar
• 7c Merz A, Kronberger J, Dunsch L, Neudeck A, Petr A, Parkanyi L. Angew. Chem. Int. Ed. 1999; 38: 1442
  CrossrefPubMedSearch in Google Scholar
• 7d Boger DL, Hong J. J. Am. Chem. Soc. 2001; 123: 8515
  CrossrefPubMedSearch in Google Scholar
• 7e Gao G.-Y, Colvin AJ, Chen Y, Zhang XP. Org. Lett. 2003; 5: 3261
  CrossrefPubMedSearch in Google Scholar
• 7f Merz A, Anikin S, Lieser B, Heinze J, John H. Chem. Eur. J. 2003; 9: 449
  CrossrefPubMedSearch in Google Scholar
• 7g Fürstner A. Angew. Chem. Int. Ed. 2003; 42: 3582
  CrossrefPubMedSearch in Google Scholar
• 7h Bonauer C, Zabel M, König B. Org. Lett. 2004; 6: 1349
  CrossrefPubMedSearch in Google Scholar
• 7i Kruppa M, Bonauer C, Michlov V, Knig B. J. Org. Chem. 2005; 70: 5305
  CrossrefPubMedSearch in Google Scholar
• 7j Hill L, Imam SH, McNab H, O’Neill WJ. Synthesis 2009; 2535
• 7k Rana A, Panda PK. Tetrahedron Lett. 2011; 52: 2697
  CrossrefSearch in Google Scholar
• 7l Sun S.-q, Cheng J, Wang Y.-j, Zhu C.-j, Xu W, Liu X.-x. Anhui Nongye Kexue 2012; 40: 12633
  Search in Google Scholar
• 7m Zahng M, Fang X, Neumann H, Beller M. J. Am. Chem. Soc. 2013; 135: 11384
  CrossrefPubMedSearch in Google Scholar
• 7n Danevčič T, Borić Vezjak M, Zorec M, Stopar D. PLoS One 2016; 11: e0162412
  CrossrefPubMedSearch in Google Scholar
• 8a Berlin A, Pagani GA, Schiavon G, Zotti G. J. Chem. Soc., Perkin Trans. 2 1990; 699
  Crossref
• 8b Boiadjiev SE, Lightner DA. J. Org. Chem. 1998; 63: 6220
  CrossrefPubMedSearch in Google Scholar
• 8c Alemán C, Domingo VM, Julia L. J. Phys. Chem. A 2001; 105: 5266
  CrossrefSearch in Google Scholar
• 8d Domingo VM, Brillas E, Torrelles X, Rius J, Julia L. J. Org. Chem. 2001; 66: 8236
  CrossrefPubMedSearch in Google Scholar
• 8e Rosa A, Ricciardi G, Baerends EJ, Zimin M, Rodgers MA. J, Matsumoto S, Ono N. Inorg. Chem. 2005; 44: 6609
  CrossrefPubMedSearch in Google Scholar
• 8f Li H, Lambert C, Stahl R. Macromolecules 2006; 39: 2049
  CrossrefSearch in Google Scholar
• 8g Thamyongkit P, Bhise AD, Taniguchi M, Lindsey JS. J. Org. Chem. 2006; 71: 903
  CrossrefPubMedSearch in Google Scholar
• 8h Loudet A, Burgess K. Chem. Rev. 2007; 107: 4891
  CrossrefPubMedSearch in Google Scholar
• 8i Peng L, Zhang X, Ma J, Zhong Z, Wang J. Org. Lett. 2007; 9: 1445
  CrossrefPubMedSearch in Google Scholar
• 8j Misra NC, Panda K, Ila H, Junjappa H. J. Org. Chem. 2007; 72: 1246
  CrossrefPubMedSearch in Google Scholar
• 8k Yin G, Wang Z, Chen A, Gao M, Wu A, Pan Y. J. Org. Chem. 2008; 73: 3377
  CrossrefPubMedSearch in Google Scholar
• 8l Gillis HM, Greene L, Thompson A. Synlett 2009; 112
• 8m Heinze J, Frontana-Uribe BA, Ludwigs S. Chem. Rev. 2010; 110: 4724
  CrossrefPubMedSearch in Google Scholar
• 8n Belviso S, Santoro E, Lelj F, Casarini D, Villani C, Franzini R, Superchi S. Eur. J. Org. Chem. 2018; 4029
  Crossref
• 8o Xu W, Hei Y.-Y, Song J.-L, Zhan X.-C, Zhang X.-G, Deng C.-L. Synthesis 2019; 51: 545
  Thieme ConnectSearch in Google Scholar
• 9a Fegley MF, Bortnick NM, McKeever LH. J. Am. Chem. Soc. 1957; 79: 4144
  CrossrefSearch in Google Scholar
• 9b Kalaycioglu E, Toppare L, Yagci Y. Synth. Met. 2000; 108: 1
  CrossrefSearch in Google Scholar
• 9c Brandsma L, Nedolya NA, Tolmachev SV. Chem. Heterocycl. Compd. 2002; 38: 54
  CrossrefSearch in Google Scholar
• 9d Nedolya NA, Brandsma L, Tolmachev SV. Russ. J. Org. Chem. 2002; 38: 907
  CrossrefSearch in Google Scholar
• 9e Nedolya NA, Brandsma L, Shlyakhtina NI. Russ. J. Org. Chem. 2002; 38: 1070
  CrossrefSearch in Google Scholar
• 9f Uyar T, Toppare L, Hacaloğlu J. J. Anal. Appl. Pyrolysis 2003; 68–69: 15
  CrossrefSearch in Google Scholar
• 9g Sadykov EK, Lobanova NA, Stankevich VK. Synthesis 2015; 47: 672
  Thieme ConnectSearch in Google Scholar
• 9h Sadykov EK, Lobanova NA, Stankevich VK. Russ. J. Org. Chem. 2016; 52: 533
  CrossrefSearch in Google Scholar
• 10a Trofimov BA. Vinylpyrroles, Chapter 2: Pyrroles. In The Chemistry of the Heterocyclic Compounds, Vol. 48. Jones RA. Wiley; New York: 1992: 131
  CrossrefSearch in Google Scholar
• 10b Trofimov BA, Mikhaleva AI, Morozova LV. Russ. Chem. Rev. 1985; 54: 609
  CrossrefSearch in Google Scholar
• 10c Settambolo R, Caiazzo A, Lazzaroni R. J. Organomet. Chem. 1996; 506: 337
  CrossrefSearch in Google Scholar
• 10d Caiazzo A, Settambolo R, Uccello-Barretta G, Lazzaroni R. J. Organomet. Chem. 1997; 548: 279
  CrossrefSearch in Google Scholar
• 10e DuBois CJ. Jr, McCarley RL. J. Electroanal. Chem. 1998; 454: 99
  CrossrefSearch in Google Scholar
• 10f Varlamov AV, Borisova TN, Voskressensky LG, Brook AA, Chernyshev AI. ARKIVOC 2000; : 147
  Crossref
• 10g Pinho e Melo TM. V. D, Soares MI. L, Rocha Gonsalves AM. d'A, Paixão JA, Beja AM, Silva MR. J. Org. Chem. 2005; 70: 6629
  CrossrefPubMedSearch in Google Scholar
• 10h Trofimov BA, Markova MV, Morozova LV, Shmidt EYu, Senotrusova EYu, Myachina GF, Myachin YuA, Vakul’skaya TI, Mikhaleva AI. Polym. Sci. Ser. B 2007; 49: 292
  CrossrefSearch in Google Scholar
• 10i Morozova LV, Tatarinova IV, Markova MV, Vasil’tsov AM, Ivanov AV, Vakul’skaya TI, Mikhaleva AI, Trofimov BA. Russ. Chem. Bull. Int. Ed. 2007; 56: 2209
  CrossrefSearch in Google Scholar
• 10j Trofimov BA, Mikhaleva AI, Shmidt EYu, Sobenina LN. Pyrroles and N-Vinylpyrroles from Ketones and Acetylenes: Recent Studies . In Advances in Heterocyclic Chemistry, Vol. 99. Katritzky AR. Academic Press; New York: 2010: 209
  Search in Google Scholar
• 10k Trofimov BA, Markova MV, MorozovaL V, Mikhaleva AI, Shmidt EYu, Zorina NV, Hyun SH. Polym. Sci. Ser. B 2010; 52: 193
  CrossrefSearch in Google Scholar
• 10l Trofimov BA, Markova MV, Morozova LV, Mikhaleva AI, Sobenina LN, Petrova OV, Vakul’skaya TI, Myachina GF, Petrushenko KB. Synth. Met. 2010; 160: 1539
  CrossrefSearch in Google Scholar
• 10m Luo J, Qin J, Kang H, Ye C. Chem. Mater. 2001; 13: 927
  CrossrefSearch in Google Scholar
• 10n Afonin AV, Pavlov DV, Albanov AI, Tarasova OA, Nedolya NA. Magn. Reson. Chem. 2013; 51: 414
  CrossrefPubMedSearch in Google Scholar
• 10o Molchanov AP, Savinkov RS, Stepakov AV, Starova GL, Kostikov RR, Barnakova VS, Ivanov AV. Synthesis 2014; 46: 771
  Thieme ConnectSearch in Google Scholar
• 11a Tarasova OA, Nedolya NA, Vvedensky VYu, Brandsma L, Trofimov BA. Tetrahedron Lett. 1997; 38: 7241
  CrossrefSearch in Google Scholar
• 11b Nedolya NA, Brandsma L, Tarasova OA, Verkruijsse HD, Trofimov BA. Tetrahedron Lett. 1998; 39: 2409
  CrossrefSearch in Google Scholar
• 11c Brandsma L, Nedolya NA, Trofimov BA. Eur. J. Org. Chem. 1999; 2663
  Crossref
• 11d Brandsma L, Nedolya NA, Tarasova OA, Trofimov BA. Chem. Heterocycl. Compd. 2000; 36: 1241
  CrossrefSearch in Google Scholar
• 11e Nedolya NA, Brandsma L, Tolmachev SV. Chem. Heterocycl. Compd. 2002; 38: 745
  CrossrefSearch in Google Scholar
• 11f Brandsma L, Nedolya NA. Synthesis 2004; 735
  Thieme Connect
• 11g Nedolya NA, Brandsma L. Russ. J. Org. Chem. 2006; 42: 607
  CrossrefSearch in Google Scholar
• 11h Nedolya NA, Brandsma L, Tarasova OA, Albanov AI, Trofimov BA. Russ. J. Org. Chem. 2011; 47: 659
  CrossrefSearch in Google Scholar
• 11i Nedolya NA, Tarasova OA, Albanov AI, Trofimov BA. Synthesis 2016; 48: 4278
  Thieme ConnectSearch in Google Scholar
• 11j Tarasova OA, Nedolya NA, Albanov AI, Trofimov BA. Eur. J. Org. Chem. 2018; 5961
  Crossref
• 11k Tarasova OA, Nedolya NA, Albanov AI, Trofimov BA. Synthesis 2019; 51: 3697
  Thieme ConnectSearch in Google Scholar
• 11l Tarasova OA, Nedolya NA, Albanov AI, Trofimov BA. ChemistrySelect 2020; 5: 5726
  CrossrefSearch in Google Scholar
• 11m Tarasova OA, Nedolya NA, Albanov AI, Bagryanskaya IYu, Trofimov BA. J. Organomet. Chem. 2021; 933: 121651
  CrossrefSearch in Google Scholar
• 12a Reppe W. Liebigs Ann. Chem. 1956; 601: 81
  CrossrefSearch in Google Scholar
• 12b Tzalis D, Koradin C, Knochel P. Tetrahedron Lett. 1999; 40: 6193
  CrossrefSearch in Google Scholar
• 12c Trofimov BA, Sobenina LN, Mikhaleva AI, Ushakov IA, Vakul’skaya TI, Stepanova ZV, Toryashinova D.-SD, Mal’kina AG, Elokhina VN. Synthesis 2003; 1272
• 12d Verma AK, Joshi M, Singh VP. Org. Lett. 2011; 13: 1630
  CrossrefPubMedSearch in Google Scholar
• 12e Patel M, Saunthwal RK, Verma AK. Acc. Chem. Res. 2017; 50: 240
  CrossrefPubMedSearch in Google Scholar
• 12f Trofimov BA, Tarasova OA, Shemetova MA, Afonin AV, Klyba LV, Baikalova LV, Mikhaleva AI. Russ. J. Org. Chem. 2003; 39: 408
  CrossrefSearch in Google Scholar
• 13a Gonzales C, Greenhouse R, Tallabs R. Can. J. Chem. 1983; 61: 1697
  CrossrefSearch in Google Scholar
• 13b Settambolo R, Mariani M, Caiazzo A. J. Org. Chem. 1998; 63: 10022
  CrossrefSearch in Google Scholar
• 13c Abele E, Dzenitis O, Rubina R, Lukevics E. Chem. Heterocycl. Compd. 2002; 38: 682
  CrossrefSearch in Google Scholar
• 13d Di Santo R, Tafi A, Costi R, Botta M, Artico M, Corelli F, Forte M, Caporuscio F, Angiolella L, Palamara AT. J. Med. Chem. 2005; 48: 5140
  CrossrefPubMedSearch in Google Scholar
• 13e Wang W, Yu D, Tian F. Synth. Met. 2008; 158: 717
  CrossrefSearch in Google Scholar
• 13f Petrova OV, Markova MV, Sobenina LN, Morozova LV, Mikhaleva AI, Hyun SH, Trofimov BA. Russ. Chem. Bull. 2009; 58: 115
  CrossrefSearch in Google Scholar
• 13g Lan T, Chen X, Liu Z, Mao Z. J. Heterocycl. Chem. 2013; 50: 1094
  CrossrefSearch in Google Scholar
• 14a Lebedev AY, Izmer VV, Kazyul’kin DN, Beletskaya IP, Voskoboynikov AZ. Org. Lett. 2002; 4: 623
  CrossrefPubMedSearch in Google Scholar
• 14b Taillefer M, Ouali A, Renard B, Spindler J.-F. Chem. Eur. J. 2006; 12: 5301
  CrossrefPubMedSearch in Google Scholar
• 14c Liao Q, Wang Y, Zhang L, Xi C. J. Org. Chem. 2009; 74: 6371
  CrossrefPubMedSearch in Google Scholar
• 15 Movassaghi M, Ondrus AE. J. Org. Chem. 2005; 70: 8638
  CrossrefPubMedSearch in Google Scholar
• 16 Kukharev BF, Stankevich VK, Kukhareva VA. Russ. J. Org. Chem. 2011; 47: 614
  CrossrefSearch in Google Scholar
• 17 Nedolya NA, Tarasova OA, Albanov AI, Trofimov BA. Tetrahedron Lett. 2010; 51: 5316
  CrossrefSearch in Google Scholar
• 18 Albano VG, Gualandi A, Monari M, Savoia D. J. Org. Chem. 2008; 73: 8376
  CrossrefPubMedSearch in Google Scholar
• 19a Mikhaleva AI, Shmidt EYu, Ivanov AV, Vasil’tsov AM, Senotrusova EYu, Protsuk NI. Russ. J. Org. Chem. 2007; 43: 228
  CrossrefSearch in Google Scholar
• 19b Trofimov BA, Mikhaleva AI, Shmidt EYu, Sobenina LN. Adv. Heterocycl. Chem. 2010; 99: 209
  CrossrefSearch in Google Scholar
• 19c Vasil’tsov AM, Ivanov AV, Mikhaleva AI, Trofimov BA. Tetrahedron Lett. 2010; 51: 1690
  CrossrefSearch in Google Scholar
• 19d Trofimov BA, Mikhaleva AI, Shmidt EYu, Sobenina LN. Chemistry of Pyrroles . CRC Press-Taylor & Fransis Group; Boca-Raton: 2014
  CrossrefSearch in Google Scholar
• 20 Nedolya NA, Tarasova OA, Аlbanov АI, Trofimov B. А. Russ. J. Org. Chem. 2021; 57: 486
  CrossrefSearch in Google Scholar
• 21a Trofimov BA, Parshina LN, Lavrov VI, Oparina LA. Russ. Chem. Bull. 1984; 33: 1532
  CrossrefSearch in Google Scholar
• 21b Trofimov BA, Oparina LA, Parshina LN, Lavrov VI, Grigorenko VI, Zhumabekov MK. Zh. Org. Khim. 1986; 22: 1583
  Search in Google Scholar
• 22a Wu X.-F, Natte K. Adv. Synth. Catal. 2016; 358: 336
  CrossrefPubMedSearch in Google Scholar
• 22b Tashrifi Z, Khanaposhtani MM, Larijani B, Mahdavi M. Adv. Synth. Catal. 2020; 362: 65
  CrossrefSearch in Google Scholar
• 23a Brandsma L. Best Synthetic Methods: Synthesis of Acetylenes, Allenes and Cumulenes: Methods and Techniques. Elsevier; Amsterdam: 2004
  Search in Google Scholar
• 23b Verkruijsse HD, Bos HJ. T, de Noten LJ, Brandsma L. Recl. Trav. Chim. Pays-Bas 1981; 100: 244
  CrossrefSearch in Google Scholar
• 24a Trofimov BA, Nedolya NA, Gerasimova VV, Voronkov MG. Sulfur Lett. 1988; 8: 73
  Search in Google Scholar
• 24b Trofimov BA, Nedolya NA, Papsheva NP, Gerasimova VV, Voronkov MG. Zh. Org. Khim. 1988; 24: 1771 ; Chem. Abstr. 1989, 110, 74812c
  Search in Google Scholar

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