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DOI: 10.1055/a-2062-8680
Oxidative C–N Bond Cleavage of Cyclic Amines with Ammonium Hypochlorite
This research was supported by the Japan Society for the Promotion of Science (JSPS KAKENHI: 22K06528, 22K15255, and 19K05459).
Abstract
An oxidative C–N bond cleavage of cyclic amines has been developed under metal-free conditions, providing N-Cl-ω-amino acids in moderate to excellent yields. The reactions proceed by using tetramethylammonium hypochlorite (TMAOCl) as an oxidant even on a gram scale. Hofmann–Löffler–Freytag-type reaction of N-Cl-ω-amino acids to form cyclic amino acids has also been demonstrated.
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Aliphatic nitrogen heterocycles such as piperidine and pyrrolidine are prevalent structural motifs in a number of natural products and biologically active compounds. Considerable effort has been made to develop efficient methods for C–H bond functionalization of N-heterocycles.[1] On the other hand, C–N bond-cleavage reactions have attracted attention as a different mode for functionalization of N-heterocycles.[2] Among them, oxidative C–N bond-cleavage reactions of N-heterocycles would be a powerful strategy to access remotely functionalized amines, which would serve as valuable intermediates to increase molecular complexity as well as to achieve skeletal diversification.[3] A number of C–N bond-cleavage reactions have been developed with stoichiometric[4] or catalytic[5] amount of metal reagents. While these methods provided valuable N-containing compounds with high efficiency, the development of analogous reactions under metal-free conditions would be desirable in terms of green chemistry. Photochemical[6] and electrochemical[7] approaches would be attractive alternatives. In addition, chemical oxidant-mediated reactions would be promising methods. For example, benzylic C–N bond-cleavage reactions have been developed by utilizing oxone®/HBr[8] or tert-butyl nitrite/O2 [9] systems (Scheme [1a]). Although tert-butyl nitrite has also been employed in non-benzylic C–N bond-cleavage reactions, these conditions are only applicable for the transformation of N-aryl-substituted heterocycles (Scheme [1b]).[10]
Hypochlorite salts are one of the classical and versatile oxidants.[11] Hypochlorite salt-mediated oxidations have often been performed with additives such as KBr[12] or phase-transfer catalysts[13] to improve reaction efficiency. Tetramethylammonium hypochlorite (TMAOCl), which is prepared by addition of chlorine to tetramethylammonium hydroxide, is a unique hypohalite salt requiring no additional phase-transfer reagents.[14] While TMAOCl has been used for the cleaning process of microelectronics substrates such as silicon wafers in the semiconductor industry,[15] the synthetic utility of TMAOCl in organic chemistry has been underexplored.[16] Herein, we report the oxidative C–N bond cleavage of N-protected cyclic amines with TMAOCl as an oxidant to provide N-Cl-ω-amino acid derivatives (Scheme [1c]).
a Determined by 1H NMR analysis using DMF as internal standard; isolated yield given in parentheses.
b Reaction was performed at room temperature.
c NaOCl (6 equiv).
d NaOCl (6 equiv) and Me4NCl (6 equiv).
We began our investigations by optimizing the reaction conditions for the C–N bond cleavage using N-Ts-piperidine (1a) as a model substrate (Table [1]). When 1a (0.5 mmol) was treated with TMAOCl (3 equiv) in the presence of TFA (3 equiv) at 0 °C, the desired product 2a was obtained in 24% yield (entry 1). Varied amounts of the oxidant and acid were investigated (entries 2–4), and the use of TMAOCl (6 equiv) with TFA (8 equiv) led to the highest yield (64%) of the desired product (entry 3). Screening of Brønsted acids revealed that TFA was the most suitable acid for this oxidation (entries 5–8). While the reaction in PhCl also provided 2a in comparable yield, the use of THF, EtOAc, and MeCN resulted in a decrease in the yield (entries 9–12). Conducting the reaction at room temperature had no positive effect on the outcome (entry 13). A commercially available NaOCl solution (available chlorine: 10.9 wt%) was found to be a less effective oxidant for this C–N bond cleavage, even when the reaction was carried out with Me4NCl (entry 3 vs. entries 14 and 15).
Next, the influence of the N-protecting groups on the reaction outcome was investigated under the optimized reaction conditions (Table [1], entry 3); the results are summarized in Table [2]. p-Nosyl-protected piperidine did not undergo the oxidation under the present reaction conditions, and the unreacted starting material was completely recovered (entry 2). An acetyl protecting group was not suitable for the present transformation (entry 3). The installation of a methoxycarbonyl (Moc) protecting group resulted in the formation of the corresponding product 2d in 99% yield (entry 4).
 |
|||
|
Entry |
PG |
2 |
Yield (%) |
|
1 |
Ts |
2a |
64 |
|
2 |
p-Ns |
2b |
0 |
|
3 |
Ac |
2c |
25 |
|
4 |
Moc |
2d |
99 |
A range of cyclic amines were examined in the oxidative cleavage reaction using TMAOCl (6 equiv) and TFA (8 equiv), as shown in Scheme [2]. N-Protected pyrrolidines participated well in this transformation, affording the corresponding products 2e and 2f in high to excellent yields. A seven-membered cyclic amine provided the desired product 2g in 87% yield. The reaction of 4-pipecoline derivatives with either Ts or Moc groups proceeded smoothly to afford the desired products 2h and 2i in good to excellent yields. Moreover, ester groups were tolerated under the present reaction conditions (2j–l). Piperidines bearing methoxy or halogen substituents were transformed into the corresponding products 2m and 2n in 93 and 71% yield, respectively. The C–N bond cleavage of N-Ts-2-methylpyrrolidine (1o) proceeded selectively at the C2 position, providing amino ketone 2o in 92% yield.
Next, the oxidative C–N bond cleavage of piperidines bearing pendant hydroxy groups was explored (Scheme [3]). The reaction of N-Moc-4-hydroxymethyl piperidine (1p) under the optimized reaction conditions led to the formation of β-substituted lactone (2p) in moderate yield. N-Moc-piperidine, with a tertiary hydroxy group, was also converted into the corresponding lactone 2q in 97% yield.
The oxidative cleavage of N-protected piperidines was readily performed on gram scales, providing 2a and 2d in 58 and 96% yield, respectively (Scheme [4a]). The synthetic utility of the present reaction was also demonstrated by the transformation of the N-Cl-ω-amino acids into cyclic amino acids by Hofmann–Löffler–Freytag-type cyclization (Scheme [4b]).[17] N-Ts-proline (3a) was obtained in 64% yield by the one-pot, two-step sequence of chlorine atom migration through the 1,5-hydrogen atom transfer using 1,1′-azobis(cyclohexane-1-carbonitrile) (V-40), followed by intramolecular cyclization under basic conditions. A similar reaction protocol starting from 2g provided 2-pyrrolidineacetic acid 3g by employing sodium hydride for the cyclization step, which was isolated as ester 3g′ by treating with TMS-diazomethane.
To gain insight into the reaction mechanism, a series of control experiments were conducted (Scheme [5]). When N-Moc-2-hydroxypiperidine (4a) was subjected to the reaction conditions, amino acid 2d was obtained in 97% yield (Scheme [5a]). In addition, N-chlorination of amino acids 4b proceeded smoothly with a TMAOCl/TFA system (Scheme [5b]). These results suggested that 4a and 4b might be possible intermediates in this transformation.
Based on the experimental results and previous reports,[18] a plausible reaction mechanism for this C–N bond cleavage of cyclic amines with TMAOCl was proposed (Scheme [6]). First, oxidation of the α-position of N-Moc-piperidine 1d with HOCl, which would be generated from TMAOCl and TFA, might provide 2-hydroxypiperidine 4a through nucleophilic attack of H2O on the iminium ion species. Then, 2-hydroxypiperidine 4a might tautomerize to ω-amino aldehyde A, which undergoes consecutive oxidation to furnish N-chlorinated amino acid 2d.
In summary, we developed the oxidative C–N bond cleavage of N-protected cyclic amines for the synthesis of N-chlorinated amino acid derivatives by using TMAOCl as an oxidant. TMAOCl exhibited a higher reaction efficiency in the present reaction compared with the combination of NaOCl/Me4NCl, which might indicate that TMAOCl serves as a promising alternative hypochlorite salt in organic synthesis. A variety of N-chlorinated amino acids were obtained in good to excellent yields even on a gram scale. The obtained compound was converted into cyclic amino acids by chlorine migration followed by intramolecular cyclization, which demonstrates the potential synthetic utility of the present reaction.
Melting points (mp) were measured with a Yanako Micro Melting Point Apparatus and reported without correction. 1H and 13C NMR spectra were recorded with a JEOL JNM-ECZ400R (400 MHz for 1H NMR, 100 MHz for 13C NMR). Chemical shift values are expressed in parts per million (ppm) relative to internal TMS (δ = 0.00 ppm for 1H NMR) or deuterated solvent peaks (δ = 77.0 ppm (CDCl3) and δ = 39.5 ppm (DMSO-d 6) for 13C NMR). Abbreviations are as follows: s, singlet; d, doublet; t, triplet; q, quartet; m, multiplet; br, broad; app, apparent. High-resolution mass spectra (HRMS) were obtained with JEOL JMS-T100TD (DART or ESI) spectrometers. The products were isolated by silica gel column chromatography (CHROMATOREX 60B, Fuji silysia). Infrared (IR) spectra were recorded with a SHIMADZU IRAffinity-1 spectrometer and expressed as frequency of absorption (cm–1).
Commercially available chemicals were purchased from Sigma–Aldrich, Tokyo Chemical Industry Co., Ltd., and FUJIFILM Wako Pure Chemical Corporation and used as received. Tetramethylammonium hypochlorite (TMAOCl) was prepared by reacting an aqueous solution of tetramethylammonium hydroxide with chlorine gas.[19] Compounds 1a,[20] 1b,[21] 1c,[22] and 1f [23] were synthesized according to the reported methods, as were compounds 1d,[23] 1e,[20] 1g,[20] 1h,[20] and 1i.[23]
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Synthesis of 1j–k; General Procedure
To a solution of ethyl diethylphosphonoacetate (1.23 g, 5.5 mmol) in THF (10 mL) was added NaH (60% in mineral oil, 220 mg, 5.5 mmol) at 0 °C. The mixture was stirred for 30 min at r.t., and N-protected 4-piperidone (5 mmol) in THF (6.7 mL) was added dropwise. After stirring for 2 h at r.t., the reaction was quenched with H2O, and the resulting mixture was extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give the corresponding α,β-unsaturated ester. To a suspension of 10% Pd/C (10 mol% Pd) in EtOH (0.25 M) was added the α,β-unsaturated ester (1 equiv) in THF (0.25 M) under an argon atmosphere. The reaction vessel was evacuated and backfilled with hydrogen gas, and the mixture was stirred overnight at r.t. under a hydrogen atmosphere (1 atm). The mixture was filtered through Celite, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography to afford 1.
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Ethyl 2-(1-Tosylpiperidin-4-yl)acetate (1j)
The title compound was prepared from N-Ts-4-piperidone (1.26 g, 5 mmol) according to the general procedure. Silica gel column chromatography (hexane/EtOAc, 9:1) gave 1j.
Yield: 1.02 g (3.1 mmol, 62% (two steps)); white solid; mp 56–57 °C; Rf = 0.27 (hexane/EtOAc, 9:1).
IR (ATR): 2924, 2852, 1722, 1334, 1163, 1031, 725 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.63 (d, J = 8.2 Hz, 2 H), 7.32 (d, J = 8.0 Hz, 2 H), 4.10 (q, J = 7.2 Hz, 2 H), 3.76 (d, J = 11.7 Hz, 2 H), 2.44 (s, 3 H), 2.29–2.20 (m, 4 H), 1.78–1.67 (m, 3 H), 1.41–1.31 (m, 2 H), 1.23 (t, J = 7.2 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 171.6, 143.1, 132.6, 129.2, 127.3, 59.9, 45.8, 40.1, 31.7, 30.7, 21.1, 13.8.
HRMS (DART): m/z [M + H]+ calcd for C16H24NO4S: 326.1426; found: 326.1440.
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Methyl 4-(2-Ethoxy-2-oxoethyl)piperidine-1-carboxylate (1k)
The title compound was prepared from N-methoxycarbonyl-4-piperidone (789 mg, 5 mmol) according to the general procedure. Silica gel column chromatography (hexane/EtOAc, 9:1) gave 1k.
Yield: 681 mg (3.0 mmol, 60% (two steps)); colorless oil; Rf = 0.22 (hexane/EtOAc, 9:1).
IR (ATR): 2924, 2852, 1730, 1697, 1447, 1285, 1161, 731 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.16–4.11 (m, 4 H), 3.68 (s, 3 H), 2.81–2.75 (m, 2 H), 2.23 (d, J = 6.9 Hz, 2 H), 2.00–1.91 (m, 1 H), 1.72–1.65 (m, 3 H), 1.26 (t, J = 7.1 Hz, 3 H), 1.22–1.12 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 171.6, 155.2, 59.7, 51.8, 43.3, 40.4, 32.4, 31.1, 13.7.
HRMS (DART): m/z [M + H]+ calcd for C11H20NO4: 230.1392; found: 230.1386.
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Methyl 4-(Acetoxymethyl)piperidine-1-carboxylate (1l)
To a solution of methyl 4-(hydroxymethyl)piperidine-1-carboxylate (346 mg, 2 mmol, 1p) in CH2Cl2 (4.0 mL) was successively added pyridine (316 mg, 4 mmol) and acetyl chloride (251 mg, 3.2 mmol) at 0 °C. After stirring for 3 h at r.t., the reaction was quenched with H2O, and the resulting mixture was extracted with CH2Cl2. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 8:2) to give 1l.
Yield: 357 mg (1.66 mmol, 83%); colorless oil; Rf = 0.32 (hexane/EtOAc, 3:1).
IR (ATR): 2945, 2857, 1738, 1695, 1447, 1219, 1035, 768 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.18 (br, 2 H), 3.93 (d, J = 6.4 Hz, 2 H), 3.69 (s, 3 H), 2.76 (app br t, J = 11.6 Hz, 2 H), 2.06 (s, 3 H), 1.87–1.76 (m, 1 H), 1.72–1.69 (m, 2 H), 1.25–1.15 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 170.9, 155.8, 68.2, 52.4, 43.4, 35.3, 28.4, 20.7.
HRMS (DART): m/z [M + H]+ calcd for C10H18NO4: 216.1236; found: 216.1228.
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Methyl 4-(Methoxymethyl)piperidine-1-carboxylate (1m)
To a solution of methyl 4-(hydroxymethyl)piperidine-1-carboxylate (520 mg, 3 mmol, 1p) in THF (15 mL) was added NaH (60% in mineral oil, 480 mg, 12 mmol) at 0 °C. After stirring for 30 min at the same temperature, methyl iodide (1.70 g, 12 mmol) was added, and the mixture was stirred for an additional 1 h. The reaction was quenched with H2O, and the resulting mixture was extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 8:2) to give 1m.
Yield: 532 mg (2.84 mmol, 95%); colorless oil; Rf = 0.41 (hexane/EtOAc, 3:1).
IR (ATR): 2922, 2852, 1695, 1447, 1225, 1088, 768 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.16 (br, 2 H), 3.68 (s, 3 H), 3.33 (s, 3 H), 3.22 (d, J = 6.2 Hz, 2 H), 2.75 (app br t, J = 12.3 Hz, 2 H), 1.80–1.70 (m, 3 H), 1.20–1.10 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 155.7, 77.3, 58.6, 52.2, 43.6, 36.1, 28.7.
HRMS (DART): m/z [M + H]+ calcd for C9H18NO3: 188.1287; found: 188.1280.
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Methyl 4-(Chloromethyl)piperidine-1-carboxylate (1n)
To a solution of methyl 4-(hydroxymethyl)piperidine-1-carboxylate (346 mg, 2 mmol, 1p) in DMF (4.0 mL) was added carbon tetrachloride (1.23 g, 8 mmol) and triphenylphosphine (2.10 g, 8 mmol) at 0 °C. After stirring for 5 h at r.t., the reaction was diluted with H2O, and the resulting mixture was extracted with EtOAc. The combined organic layers were washed with brine, dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 8:2) to give 1n.
Yield: 342 mg (1.78 mmol, 89%); colorless oil; Rf = 0.41 (hexane/EtOAc, 3:1).
IR (ATR): 2993, 2947, 2854, 1692, 1446, 1236, 1190, 968, 768, 727 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.19 (br, 2 H), 3.69 (s, 3 H), 3.41 (d, J = 6.2 Hz, 2 H), 2.76 (app br t, J = 11.9 Hz, 2 H), 1.87–1.76 (m, 3 H), 1.26–1.16 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 155.6, 52.4, 49.3, 43.4, 38.4, 29.5.
HRMS (DART): m/z [M + H]+ calcd for C8H15 35ClNO2: 192.0791; found: 192.0789.
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2-Methyl-1-tosylpyrrolidine (1o)
To a solution of (1-tosylpyrrolidin-2-yl)methyl 4-methylbenzenesulfonate[24] (2.1 g, 5.1 mmol) in THF (7.3 mL) was added lithium aluminum hydride (387 mg, 10.2 mmol) at r.t. under an argon atmosphere. After stirring for 2 h at the same temperature, H2O and 1 M NaOH were successively added at 0 °C. The resulting mixture was filtrated through Celite, and the filter cake was rinsed with EtOAc. The filtrate was neutralized pH 7 with 10% aqueous HCl, and the resulting mixture was extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 8:2) to afford 1o.
Yield: 880 mg (3.68 mmol, 72%); white solid.
1H NMR (400 MHz, CDCl3): δ = 7.72 (d, J = 8.2 Hz, 2 H), 7.31 (d, J = 7.8 Hz, 2 H), 3.73–3.69 (m, 1 H), 3.47–3.41 (m, 1 H), 3.17–3.11 (m, 1 H), 2.43 (s, 3 H), 1.86–1.79 (m, 1 H), 1.71–1.64 (m, 1 H), 1.54–1.46 (m, 2 H), 1.31 (d, J = 5.9 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 143.0, 134.5, 129.4, 127.2, 55.9, 48.9, 33.2, 23.7, 22.7, 21.3.
The 1H and 13C spectra are in accordance with reported data.[25]
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Methyl 4-(Hydroxymethyl)piperidine-1-carboxylate (1p)
To a solution of 4-piperidinemethanol (1.38 g, 12 mmol) in CH2Cl2 (24 mL) was successively added Et3N (1.82 g, 18 mmol) and methyl chloroformate (1.36 g, 14.4 mmol) at 0 °C. After stirring for 3 h at r.t., the reaction was quenched with H2O, and the resulting mixture was extracted with CH2Cl2. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 1:1) to give 1p.
Yield: 1.65 g (9.52 mmol, 79%); colorless oil; Rf = 0.17 (hexane/EtOAc, 2:1).
IR (ATR): 3420, 2918, 2857, 1676, 1447, 1248, 1213, 1036, 768 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.19 (br, 2 H), 3.69 (s, 3 H), 3.51 (d, J = 6.2 Hz, 2 H), 2.76 (app br t, J = 11.6 Hz, 2 H), 1.76–1.62 (m, 3 H), 1.21–1.11 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 155.9, 67.4, 52.5, 43.7, 38.6, 28.5.
HRMS (DART): m/z [M + H]+ calcd for C8H16NO3: 174.1130; found: 174.1126.
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Synthesis of Methyl 4-(2-Hydroxypropan-2-yl)piperidine-1-carboxylate (1q) from 1q′
To a solution of 1-(methoxycarbonyl)piperidine-4-carboxylic acid[26] (1.46 g, 7.8 mmol) in MeOH (7.8 mL) was added thionyl chloride (316 mg, 11.7 mmol) at 0 °C. After stirring for 3 h at r.t., the reaction was quenched with H2O, and the resulting mixture was extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 8:2) to give dimethyl piperidine-1,4-dicarboxylate (1q′).
To a solution of 1q′ (402 mg, 2 mmol) in THF (10 mL) was added a solution of MeMgI [prepared from methyl iodide (852 mg, 6 mmol) and magnesium (146 mg, 6 mmol) in Et2O (2.0 mL)], dropwise at 0 °C. After stirring for 2 h at r.t., sat. aqueous NH4Cl was added at 0 °C. The resulting mixture was extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 2:1) to give 1q.
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Preparation of Dimethyl Piperidine-1,4-dicarboxylate (1q′)
Yield: 1.43 g (7.12 mmol, 91%); colorless oil; Rf = 0.32 (hexane/EtOAc, 3:1).
IR (ATR): 2953, 2859, 1730, 1695, 1447, 1173, 1038, 768 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.06 (br, 2 H), 3.69 (s, 6 H), 2.90 (app br t, J = 11.5 Hz, 2 H), 2.51–2.44 (m, 1 H), 1.91–1.88 (m, 2 H), 1.69–1.59 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 174.5, 155.5, 52.3, 51.5, 42.9, 40.5, 27.6.
HRMS (DART): m/z [M + H]+ calcd for C9H16NO4: 202.1079; found: 202.1074.
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Methyl 4-(2-Hydroxypropan-2-yl)piperidine-1-carboxylate (1q)
Yield: 355 mg (1.76 mmol, 88%); colorless oil; Rf = 0.21 (hexane/EtOAc, 2:1).
IR (ATR): 3447, 2953, 2859, 1680, 1449, 1238, 1153, 928 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.24 (br, 2 H), 3.69 (s, 3 H), 2.70 (app br t, J = 12.1 Hz, 2 H), 1.76 (app d, J = 13.0 Hz, 2 H), 1.44 (tt, J = 12.1, 3.2 Hz, 1 H), 1.28–1.18 (m, 8 H).
13C NMR (100 MHz, CDCl3): δ = 155.8, 72.0, 52.4, 47.3, 44.2, 26.8, 26.6.
HRMS (DART): m/z [M + H]+ calcd for C10H20NO4: 202.1443; found: 202.1453.
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Oxidative C–N Bond Cleavage of Cyclic Amines; General Procedure
To a solution of cyclic amine (0.5 mmol) in CH2Cl2 (0.5 mL) was successively added 8.29 wt% tetramethylammonium hypochlorite (377 mg, 2.5 mL, 3 mmol) and TFA (456 mg, 4 mmol) at 0 °C. After stirring for 24 h at the same temperature, the resulting mixture was extracted with CH2Cl2. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography to give the desired product 2.
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5-(N-Chloro-4-methylphenylsulfonamido)pentanoic Acid (2a)
Silica gel column chromatography (hexane/EtOAc, 3:1) gave 2a.
Yield: 97.8 mg (0.32 mmol, 64%); colorless oil; Rf = 0.33 (hexane/EtOAc, 1:1).
IR (ATR): 3091, 3032, 2933, 1734, 1705, 1362, 1217, 1167, 812 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.2 Hz, 2 H), 7.39 (d, J = 8.0 Hz, 2 H), 3.25 (t, J = 6.1 Hz, 2 H), 2.48 (s, 3 H), 2.44–2.40 (m, 2 H), 1.76–1.73 (m, 4 H).
13C NMR (100 MHz, CDCl3): δ = 179.3, 145.4, 129.7, 129.6, 129.5, 56.0, 33.1, 26.1, 21.7, 21.0.
HRMS (DART): m/z [M + H]+ calcd for C12H17 35ClNO4S: 306.0567; found: 306.0573.
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5-(N-Chloroacetamido)pentanoic Acid (2c)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2c.
Yield: 23.8 mg (0.123 mmol, 25%); colorless oil; Rf = 0.25 (hexane/ EtOAc, 1:1).
IR (ATR): 3080, 3009, 2938, 1726, 1666, 1389, 1165, 1094 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.73 (t, J = 6.7 Hz, 2 H), 2.41 (td, J = 7.1, 2.0 Hz, 2 H), 2.25 (s, 3 H), 1.78–1.62 (m, 4 H).
13C NMR (100 MHz, CDCl3): δ = 178.9, 172.5, 51.2, 33.4, 26.5, 21.8, 21.1.
HRMS (DART): m/z [M + H]+ calcd for C7H13 35ClNO3: 194.0584; found: 194.0582.
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5-(Chloro(methoxycarbonyl)amino)pentanoic Acid (2d)
Silica gel column chromatography (hexane/EtOAc, 1:1) gave 2d.
Yield: 103.6 mg (0.494 mmol, 99%); colorless oil; Rf = 0.38 (hexane/ EtOAc, 1:1).
IR (ATR): 3109, 2954, 1701, 1447, 1348, 1196, 914, 731 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.80 (s, 3 H), 3.65 (t, J = 6.6 Hz, 2 H), 2.41 (t, J = 7.2 Hz, 2 H), 1.79–1.63 (m, 4 H).
13C NMR (100 MHz, CDCl3): δ = 179.3, 156.4, 54.3, 33.4, 26.5, 21.0.
HRMS (DART) m/z [M + H]+ calcd for C7H13 35ClNO4: 210.0533; found: 210.0536.
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4-(N-Chloro-4-methylphenylsulfonamido)butanoic Acid (2e)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2e.
Yield: 115.5 mg (0.396 mmol, 79%); colorless oil; Rf = 0.29 (hexane/ EtOAc, 1:1).
IR (ATR): 3096, 3032, 2957, 2924, 1707, 1356, 186, 1167, 802 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.84–7.81 (m, 2 H), 7.41–7.38 (m, 2 H), 3.32 (t, J = 6.4 Hz, 2 H), 2.53 (t, J = 7.3 Hz, 2 H), 2.48 (s, 3 H), 2.05–1.98 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 178.8, 145.5, 129.7, 129.50, 129.46, 55.6, 30.1, 21.9, 21.6.
HRMS (DART): m/z [M + H]+ calcd for C11H15 35ClNO4S: 292.0410; found: 292.0422.
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4-(Chloro(methoxycarbonyl)amino)butanoic Acid (2f)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2f.
Yield: 96.8 mg (0.495 mmol, 99%); colorless oil; Rf = 0.33 (hexane/ EtOAc, 1:1).
IR (ATR): 3169, 3073, 2957, 1703, 1449, 1196, 750 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.80 (s, 3 H), 3.71 (t, J = 6.6 Hz, 2 H), 2.43 (t, J = 7.3 Hz, 2 H), 2.05–1.98 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 178.4, 156.4, 54.4, 53.1, 30.3, 22.1.
HRMS (DART): m/z [M + H]+ calcd for C6H11 35ClNO4: 196.0377; found: 196.0380.
#
6-(N-Chloro-4-methylphenylsulfonamido)hexanoic Acid (2g)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2g.
Yield: 138.5 mg (0.433 mmol, 87%); white solid; mp 106–107 °C; Rf = 0.2 (hexane/EtOAc, 1:1).
IR (ATR): 3032, 2924, 1709, 1358, 1285, 1167, 804, 663 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.5 Hz, 2 H), 7.39 (d, J = 8.0 Hz, 2 H), 3.23 (t, J = 6.7 Hz, 2 H), 2.48 (s, 3 H), 2.38 (t, J = 7.4 Hz, 2 H), 1.72–1.65 (m, 4 H), 1.47–1.42 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 179.9, 145.4, 129.7, 129.6, 129.5, 56.3, 33.8, 26.6, 25.4, 24.0, 21.7.
HRMS (DART): m/z [M + H]+ calcd for C13H19 35ClNO4S: 320.0723; found: 320.0723.
#
5-(N-Chloro-4-methylphenylsulfonamido)-3-methylpentanoic Acid (2h)
Silica gel column chromatography (hexane/EtOAc, 3:1 to 1:1) gave 2h.
Yield: 96.5 mg (0.302 mmol, 60%); white solid; mp 80–81 °C; Rf = 0.3 (hexane/EtOAc, 1:1).
IR (ATR): 3038, 2916, 1690, 1433, 1352, 1165, 812 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.2 Hz, 2 H), 7.40 (d, J = 8.2 Hz, 2 H), 3.36–3.21 (m, 2 H), 2.48 (s, 3 H), 2.43–2.36 (m, 1 H), 2.26 (dd, J = 15.3, 6.0 Hz, 1 H), 2.14 (dd, J = 15.3, 7.6 Hz, 1 H), 1.84–1.76 (m, 1 H), 1.63–1.56 (m, 1 H), 1.03 (d, J = 6.6 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 178.8, 145.4, 129.7, 129.6, 129.5, 54.4, 40.9, 33.1, 27.1, 21.7, 19.3.
HRMS (DART): m/z [M + H]+ calcd for C13H19 35ClNO4S: 320.0723; found: 320.0738.
#
5-(Chloro(methoxycarbonyl)amino)-3-methylpentanoic Acid (2i)
Silica gel column chromatography (hexane/EtOAc, 1:1) gave 2i.
Yield: 107.4 mg (0.48 mmol, 96%); colorless oil; Rf = 0.35 (hexane/ EtOAc, 1:1).
IR (ATR): 3179, 2958, 1701, 1446, 1229, 1193, 750 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.80 (s, 3 H), 3.69 (t, J = 7.2 Hz, 2 H), 2.41 (dd, J = 15.2, 5.8 Hz, 1 H), 2.23 (dd, J = 15.2, 8.0 Hz, 1 H), 2.07–1.99 (m, 1 H), 1.83–1.74 (m, 1 H), 1.63–1.54 (m, 1 H), 1.03 (d, J = 6.6 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 178.5, 156.3, 54.3, 52.1, 41.1, 33.5, 27.1, 19.4.
HRMS (DART): m/z [M + H]+ calcd for C8H15 35ClNO4: 224.0690; found: 224.0682.
#
3-(2-(N-Chloro-4-methylphenylsulfonamido)ethyl)-5-ethoxy-5-oxopentanoic Acid (2j)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2j.
Yield: 105.2 mg (0.268 mmol, 54%); colorless oil; Rf = 0.5 (hexane/ EtOAc, 1:1).
IR (ATR): 3034, 2974, 2920, 1721, 1703, 1167, 1153, 810 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.82 (d, J = 8.2 Hz, 2 H), 7.40 (d, J = 8.2 Hz, 2 H), 4.14 (q, J = 7.2 Hz, 2 H), 3.36–3.25 (m, 2 H), 2.53–2.47 (m, 8 H), 1.84–1.80 (m, 2 H), 1.26 (t, J = 7.1 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 177.5, 172.0, 145.6, 129.8, 129.6, 129.5, 60.6, 54.2, 37.7, 37.3, 30.3, 28.8, 21.7, 14.2.
HRMS (DART): m/z [M + H]+ calcd for C16H23 35ClNO6S: 392.0935; found: 392.0918.
#
3-(2-(Chloro(methoxycarbonyl)amino)ethyl)-5-ethoxy-5-oxopentanoic Acid (2k)
Silica gel column chromatography (hexane/EtOAc, 3:1 to 1:1) gave 2k.
Yield: 77.8 mg (0.263 mmol, 53%); colorless oil; Rf = 0.45 (hexane/ EtOAc, 1:1).
IR (ATR): 3240, 2957, 1703, 1447, 1177, 1159, 1028, 735 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.15 (q, J = 7.1 Hz, 2 H), 3.79 (s, 3 H), 3.75–3.66 (m, 2 H), 2.50–2.44 (m, 4 H), 2.41–2.32 (m, 1 H), 1.85–1.76 (m,2 H), 1.27 (t, J = 7.2 Hz, 3 H).
13C NMR (100 MHz, CDCl3): δ = 177.8, 172.0, 156.3, 60.5, 54.4, 51.8, 37.9, 37.6, 30.9, 28.8, 14.1.
HRMS (ESI): m/z [M + Na]+ calcd for C11H18 35ClNNaO6: 318.0720; found: 318.0712.
#
3-(Acetoxymethyl)-5-(chloro(methoxycarbonyl)amino)pentanoic Acid (2l)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2l.
Yield: 89.2 mg (0.317 mmol, 63%); colorless oil; Rf = 0.29 (hexane/ EtOAc, 2:1).
IR (ATR): 3231, 2957, 1728, 1703, 1446, 1364, 1227, 1038, 731 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.13 (dd, J = 11.3, 4.9 Hz, 1 H), 4.07 (dd, J = 11.2, 5.7 Hz, 1 H), 3.80 (s, 3 H), 3.72 (td, J = 7.0, 3.0 Hz, 2 H), 2.51–2.41 (m, 2 H), 2.31–2.22 (m, 1 H), 2.07 (s, 3 H), 1.86–1.71 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 177.8, 171.0, 156.3, 65.8, 54.4, 51.8, 35.8, 31.5, 28.6, 20.7.
HRMS (DART): m/z [M + H]+ calcd for C10H17 35ClNO6: 282.0744; found: 282.0750.
#
5-(Chloro(methoxycarbonyl)amino)-3-(methoxymethyl)pentanoic Acid (2m)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2m.
Yield: 118.2 mg (0.466 mmol, 93%); colorless oil; Rf = 0.22 (hexane/ EtOAc, 2:1).
IR (ATR): 3032, 2955, 2930, 1705, 1449, 1354, 1196, 1096, 907, 648 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.79 (s, 3 H), 3.70 (t, J = 7.1 Hz, 2 H), 3.42–3.32 (m, 5 H), 2.51 (dd, J = 16.0, 7.3 Hz, 1 H), 2.39 (dd, J = 16.0, 5.9 Hz, 1 H), 2.21–2.11 (m, 1 H), 1.85–1.70 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 178.2, 156.3, 74.5, 58.8, 54.3, 52.0, 36.1, 32.4, 28.8.
HRMS (DART): m/z [M + H]+ calcd for C9H17 35ClNO5: 254.0795; found: 254.0807.
#
5-(Chloro(methoxycarbonyl)amino)-3-(chloromethyl)pentanoic Acid (2n)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2n.
Yield: 91.4 mg (0.354 mmol, 71%); colorless oil; Rf = 0.50 (hexane/ EtOAc, 2:1).
IR (ATR): 3102, 3005, 2957, 1703, 1445, 1350, 1234, 1198, 1030, 910, 735, 731 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.81 (s, 3 H), 3.78–3.64 (m, 4 H), 2.63 (dd, J = 16.7, 7.8 Hz, 1 H), 2.48 (dd, J = 16.7, 5.5 Hz, 1 H), 2.37–2.28 (m, 1 H), 1.94–1.77 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 177.9, 156.4, 54.5, 51.5, 47.3, 35.7, 33.3, 28.9.
HRMS (DART): m/z [M + H]+ calcd for C8H14 35Cl2NO4: 258.0300; found: 258.0305.
#
N-Chloro-4-methyl-N-(4-oxopentyl)benzenesulfonamide (2o)
Silica gel column chromatography (hexane/EtOAc, 3:1) gave 2o.
Yield: 133.5 mg (0.461 mmol, 92%); colorless oil.
IR (ATR): 3277, 2926, 1713, 1325, 1155, 1089, 813 cm–1.
1H NMR (400 MHz, CDCl3): δ = 7.82–7.81 (m, 2 H), 7.39 (d, J = 8.7 Hz, 2 H), 3.23 (t, J = 6.2 Hz, 2 H), 2.62 (t, J = 7.0 Hz, 2 H), 2.47 (s, 3 H), 2.18 (s, 3 H), 1.96–1.90 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 207.6, 145.4, 129.6, 129.4, 129.4, 55.9, 39.2, 30.0, 21.6, 20.7.
HRMS (ESI): m/z [M + Na]+ calcd for C12H16 35ClNNaO3S: 312.0437; found: 312.0433.
#
Methyl Chloro(2-(5-oxo-tetrahydrofuran-3-yl)ethyl)carbamate (2p)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2p.
Yield: 71.2 mg (0.321 mmol, 64%); colorless oil; Rf = 0.21 (hexane/ EtOAc, 2:1).
IR (ATR): 2957, 1773, 1703, 1447, 1352, 1171, 1024, 908 cm–1.
1H NMR (400 MHz, CDCl3): δ = 4.46 (dd, J = 9.1, 7.3 Hz, 1 H), 3.98 (dd, J = 9.1, 7.1 Hz, 1 H), 3.81 (s, 3 H), 3.70 (t, J = 6.6 Hz, 2 H), 2.73–2.56 (m, 2 H), 2.25 (dd, J = 16.8, 7.9 Hz, 1 H), 1.94–1.80 (m, 2 H).
13C NMR (100 MHz, CDCl3): δ = 176.4, 156.2, 72.6, 54.5, 52.1, 34.1, 32.7, 30.3.
HRMS (DART): m/z [M + H]+ calcd for C8H13 35ClNO4: 222.0533; found: 222.0534.
#
Methyl Chloro(2-(2,2-dimethyl-5-oxo-tetrahydrofuran-3-yl)ethyl)carbamate (2q)
Silica gel column chromatography (hexane/EtOAc, 2:1) gave 2q.
Yield: 121.4 mg (0.486 mmol, 97%); colorless oil; Rf = 0.29 (hexane/ EtOAc, 2:1).
IR (ATR): 2976, 2955, 1763, 1703, 1447, 1354, 1258, 1128, 957 cm–1.
1H NMR (400 MHz, CDCl3): δ = 3.82 (s, 3 H), 3.78–3.71 (m, 1 H), 3.65–3.58 (m, 1 H), 2.70 (dd, J = 17.0, 7.9 Hz, 1 H), 2.38–2.31 (m, 1 H), 2.28–2.20 (m, 1 H), 1.96–1.88 (m, 1 H), 1.68–1.58 (m, 1 H), 1.47 (s, 3 H), 1.29 (s, 3 H).
13C NMR (100 MHz, CDCl3): δ = 175.1, 156.2, 86.3, 54.5, 52.7, 42.6, 34.6, 27.3, 27.2, 21.9.
HRMS (DART): m/z [M + H]+ calcd for C10H17 35ClNO4: 250.0846; found: 250.0844.
#
Synthesis of 3a from 2a
To a solution of 2a (61.2 mg, 0.2 mmol) in dichloroethane (2.0 mL) was added 1,1′-azobis(cyclohexane-1-carbonitrile) (V-40, 9.8 mg, 0.04 mmol) at r.t., and the mixture was heated at reflux for 5 h. After the addition of 1.0 M NaOH (1.0 mL, 1 mmol) at r.t., the reaction mixture was stirred for 2 h at the same temperature. The resulting mixture was treated with H2O and washed with CH2Cl2. The aqueous layer was acidified to pH 2.0–3.0 with 10% aqueous HCl and extracted with CH2Cl2. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (CH2Cl2/MeOH, 9:1) to afford 3a.
Yield: 34.6 mg (0.128 mmol, 64% (two steps)); white solid; mp 44–45 °C; Rf = 0.22 (CH2Cl2/MeOH, 9:1).
IR (ATR): 3049, 2881, 1714, 1337, 1150, 1103, 808, 663 cm–1.
1H NMR (400 MHz, DMSO-d 6): δ = 7.75 (d, J = 8.2 Hz, 2 H), 7.47 (d, J = 8.0 Hz, 2 H), 4.10 (dd, J = 8.0, 4.6 Hz, 1 H), 3.41–3.35 (m, 1 H), 3.20–3.14 (m, 1 H), 2.44 (s, 3 H), 1.94–1.79 (m, 3 H), 1.61–1.55 (m, 1 H).
13C NMR (100 MHz, DMSO-d 6): δ = 173.2, 143.5, 134.6, 129.9, 127.2, 60.4, 48.4, 30.4, 24.2, 21.0.
HRMS (DART): m/z [M + H]+ calcd for C12H16NO4S: 270.0800; found: 270.0795.
#
Synthesis of 3g′ from 2g
To a solution of 2g (61.2 mg, 0.2 mmol) in dichloroethane (2.0 mL) was added 1.1′-azobis(cyclohexane-1-carbonitrile) (V-40, 9.8 mg, 0.04 mmol) at r.t., and the mixture was heated at reflux for 4 h. All volatiles were removed under reduced pressure, and the residue was dried in vacuo. The crude mixture was dissolved in THF (2.0 mL), and sodium hydride (60% in mineral oil, 20 mg, 0.5 mmol) was added slowly at 0 °C. After stirring for 2 h at r.t., the reaction was quenched with H2O and the mixture was washed with CH2Cl2. The aqueous layer was acidified to pH 2.0–3.0 with 10% aqueous HCl and extracted with CH2Cl2. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was passed through a short column of silica gel (hexane/EtOAc, 1:1) to afford a mixture of 3g. The mixture was dissolved in anhyd MeOH/benzene (1.8 mL, 2:7), and trimethylsilyldiazomethane (2 M solution in hexane, 0.24 mmol) was added at r.t. After stirring for 1 h, the reaction mixture was treated with H2O and extracted with EtOAc. The combined organic layers were dried over Na2SO4, filtered, and concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane/EtOAc, 8:2) to afford 3g′.
Yield: 18.6 mg (0.062 mmol, 31% (three steps)); colorless oil.
1H NMR (400 MHz, CDCl3): δ = 7.74 (d, J = 8.0 Hz, 2 H), 7.33 (d, J = 8.0 Hz, 2 H), 3.99–3.92 (m, 1 H), 3.69 (s, 3 H), 3.48–3.43 (m, 1 H), 3.15–3.06 (m, 2 H), 2.51 (dd, J = 16.2, 10.1 Hz, 1 H), 2.44 (s, 3 H), 1.83–1.72 (m, 2 H), 1.69–1.60 (m, 1 H), 1.57–1.50 (m, 1 H).
13C NMR (100 MHz, CDCl3): δ = 171.7, 143.5, 133.9, 129.7, 127.5, 56.5, 51.6, 49.1, 41.1, 31.6, 23.7, 21.5.
The 1H and 13C NMR spectra are in accordance with reported data.[27]
#
#
Conflict of Interest
The authors declare the following competing financial interest: One of the authors (H.N.) belongs to Tokuyama Corporation.
Acknowledgment
The spectral data was collected with the research equipment shared in the MEXT Project for promoting public utilization of advanced research infrastructure (Program for supporting introduction of the new sharing system: JPMXS0422500320). We thank Tokuyama Corporation for the generous gift of tetramethylammonium hypochlorite.
Supporting Information
- Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/a-2062-8680.
- Supporting Information
-
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Corresponding Authors
Publication History
Received: 31 January 2023
Accepted after revision: 27 March 2023
Accepted Manuscript online:
27 March 2023
Article published online:
24 April 2023
© 2023. Thieme. All rights reserved
Georg Thieme Verlag KG
Rüdigerstraße 14, 70469 Stuttgart, Germany
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References
- 1a Campos KR. Chem. Soc. Rev. 2007; 36: 1069
- 1b Mitchell EA, Peschiulli A, Lefevre N, Meerpoel L, Maes BU. W. Chem. Eur. J. 2012; 18: 10092
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- 1f He Y, Zheng Z, Yang J, Zhang X, Fan X. Org. Chem. Front. 2021; 8: 4582
- 2a Shawcross AP, Stanforth SP. J. Heterocycl. Chem. 1990; 27: 367
- 2b Han G, McIntosh MC, Weinreb SM. Tetrahedron Lett. 1994; 35: 5813
- 2c Van Betsbrugge J, Van Den Nest W, Verheyden P, Tourwé D. Tetrahedron 1998; 54: 1753
- 2d Honda T, Ishikawa F. Chem. Commun. 1999; 1065
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