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DOI: 10.1055/s-0037-1611793
1,10-Phenanthroline- or Electron-Promoted Cyanation of Aryl Iodides
This work was supported in part by JSPS KAKENHI Grant Numbers JP16K05695, JP16K05777, JP16H01155, and JP18H04415 in Middle Molecular Strategy.
Publication History
Received: 05 February 2019
Accepted after revision: 24 March 2019
Publication Date:
11 April 2019 (online)
Published as part of the Cluster Electrochemical Synthesis and Catalysis
Abstract
A 1,10-phenanthroline-promoted cyanation of aryl iodides has been developed. 1,10-Phenanthroline worked as an organocatalyst for the reaction of aryl iodides with tetraalkylammonium cyanide to afford aryl cyanides. A similar reaction occurred through an electroreductive process.
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The aryl cyanide group is a significant motif in many pharmaceuticals, natural products, and organic materials.[1] Aryl cyanides are also important as precursors because the nitrile group can be transformed into a wide variety of other functional groups, such as amides, carboxylic acids, imines, ketones, or amines. Conventional methods for synthesizing aryl cyanides include the Sandmeyer reaction[2] and the Rosenmund–von Braun reaction[3] (Scheme [1]). The Sandmeyer reaction requires diazonium salts, which are sometimes explosive, whereas the Rosenmund–von Braun reaction usually requires harsh reaction conditions. Additionally, a stoichiometric amount of copper(I) cyanide needs to be used, which is often problematic in large-scale syntheses. In recent decades, transition-metal-catalyzed cyanations of aryl halides or arylboronic acids have been studied intensively.[4] [5] For instance, Buchwald and co-workers reported a copper-catalyzed Rosenmund–von Braun-type reaction.[5n,5o] Recently, cyanation reactions using nonmetallic cyanation agents have also been reported.[6] Shen and co-workers reported a palladium-catalyzed cyanation reaction that uses ethyl cyanoacetate as a cyanating agent.[6a] The Wang group reported iron-catalyzed cyanation using hypervalent iodonium salts.[6b] Yamaguchi and co-workers reported a Ni-catalyzed cyanation using aminoacetonitriles as cyanating agents.[6k]
Although there have been many other reports on cyanation reactions, most of them required the use of a stoichiometric amount of a metal cyanide or the use of a transition-metal catalyst. In contrast, there have been only a few reports on cyanation reactions by metal-free approaches.[7] Kita and co-workers reported a hypervalent-iodine-mediated direct cyanation of electron-rich heteroaromatics.[7a] [7b] A Lewis acid-catalyzed direct cyanation of indoles and pyrroles was reported by the Wang group.[7c] Nicewicz recently reported direct cyanation reactions that used photoredox catalysts.[7d] In another approach, the Novi group reported an electroreductive cyanation using diazosulfides as sources of aryl radicals.[8] Although these reactions proceeded with a catalytic amount of electricity, a large amount (20 equiv) of Bu4NCN was required for the reaction, and its scope was limited.
Meanwhile, t-BuOK- and t-BuONa-mediated cross-coupling reactions between aryl halides and arenes have received considerable attention as novel transition-metal-free cross-coupling reactions.[9] These reactions are believed to proceed by an SRN1 mechanism. A key step is single-electron transfer (SET) from t-BuOM/diamine (M = K or Na) to the aryl halide to generate an aryl radical species that reacts with an arene. We surmised that aryl radical species generated in this manner might participate in other reactions, such as cyanation. Aryl cyanides are obtained when aryl halides react with an appropriate cyanating agent. On the basis of this hypothesis, we began to study of t-BuOM-mediated cyanation reactions of aryl halides. Although the desired reactions proceeded, we unexpectedly found that t-BuOM was unnecessary and that a catalytic amount of 1,10-phenanthroline (phen) promoted the cyanation reactions. Similar reactions were realized by electroreduction. Here, we report the first phen- or electron-promoted cyanation reactions of aryl halides in a metal-free fashion.
On the basis of our preliminary hypothesis, we first carried out t-BuOM-mediated cyanation of 1-iodonaphthalene (1a) as a model compound (Table [1]). In the presence of t-BuONa (2.0 equiv) and 1,10-phenanthroline (phen, 10 mol%), iodide 1a was treated with several cyanide sources at 150 °C (Table [1], entries 1–5). NaCN and KCN were ineffective (entries 1 and 2). With Me3SiCN, the desired cyanated product 2a was obtained in 14% yield together with a 39% yield of the dehalogenated product 3a (entry 3). The use of tetraalkylammonium cyanides gave better results (entries 4 and 5). With tetrabutylammonium cyanide (Bu4NCN) or tetraethylammonium cyanide (Et4NCN), 2a was obtained in yields of 20 and 29%, respectively. The effect of the solvent was examined next. Among several solvents studied, dimethyl sulfoxide (DMSO) gave the best results. For instance, the yield of 2a decreased markedly to 6% in N,N-dimethylformamide (DMF) and to 19% in acetonitrile (MeCN). When we used t-BuOK instead of t-BuONa, we obtained 2a and 3a in similar yields (entry 6). Decreasing the amount of t-BuOK to 1.0 equivalents increased the yield of 2a to 40%. Surprisingly, the cyanation proceeded in the absence of a base, and 2a was obtained in 32% yield (entry 7).[10] This result suggested that phen itself can be used as an organocatalyst for the cyanation. Increasing the amount of phen increased the yield of 2a, and with 50 mol% of phen, 2a was obtained in 45% yield (entry 8); this reaction was complete within three hours. The use of 80 mol% of phen gave a similar result to that with 50 mol% of phen (entry 9). These results are quite different from the results of previously reported t-BuOM-mediated cross-coupling reactions, which did not proceed in the absence of t-BuOM. Although the reason is not clear at present time, the reduction potentials of the iodoarene and phen were rather close to one another [see the cyclic voltammetry results in the Supplementary Information (SI)], which would lead to SET from phen to the iodoarene.
a Determined by GC with dodecane as an internal standard.
b Not detected.
c Performed in DMF.
d Performed in MeCN.
e Performed with 1.0 equivalent of base.
f Performed with 50 mol% of phen.
g Performed for 3 h.
h Performed with 80 mol% of phen.
We focused on the unexpected phen-promoted cyanation and we optimized the conditions for this reaction. First, we screened several diamines as catalysts for the cyanation (Table [2]). Without a catalyst, the reaction did not proceed at all, and the starting material 1a was recovered quantitatively (Table [2], entry 1). 4,7-Dichloro-1,10-phenanthroline (dcphen) could also be used for the cyanation, but its efficiency was lower than that of phen (entry 2). In contrast, 3,4,7,8-tetramethylphenanthroline (tmphen), 4,7-dichlorophenanthroline (Ph-phen), 4,4′-dimethyl-2,2′-bipyridyl (dmbpy), 4,4′-di-tert-butyl-2,2′-bipyridyl (dtbpy), and N,N′-dimethylethylenediamine (DMEDA) were ineffective (entries 3–8).
a Determined by GC with dodecane as an internal standard.
b Not detected.
A problem of the reaction was that dehalogenation of the substrate competed with the desired cyanation, probably because the naphthyl radical generated from 1a partially reacted with DMSO before it reacted with Et4NCN.[11] We therefore surmised that a higher concentration would be better for the reaction. The effect of the concentration on the cyanation is summarized in Table [3]. As expected, increasing the concentration of 1a from 0.1 M to 0.3 M drastically suppressed the generation of the dehalogenated byproduct 3a, and increased the yield of 2a to 55% (Table [3], entry 2). With 0.5 M of 1a, the yield of 2a increased to 60% (entry 3). At a much higher concentration or under neat conditions, the dehalogenation was efficiently suppressed, but the yield of 2a decreased (entries 4 and 5). During the course of further optimizations, we found that the reaction was also markedly affected by the reaction temperature (entries 6 and 7). When the reaction was performed at 130 °C, the yield of 2a increased considerably (entry 6). In this case, the amount of phen could be reduced to 20 mol% and 2a was obtained in 78% isolated yield within one hour. In contrast, 2a was not obtained at 100 °C, demonstrating that precise control of the reaction temperature is important for the reaction.
a Determined by GC with dodecane as an internal standard.
b Not detected.
c Performed with 20 mol% of phen.
d Performed for 1 h; isolated yield.
With the optimized conditions, we conducted phen-promoted cyanations of several aryl halides (Scheme [2]). With 1-bromonaphthalene, nitrile 2a was obtained in 19% yield. The reaction using 1-chloronaphthalene did not give 2a at all. With iodobenzene, we obtained benzonitrile (2b) in 48% yield. p-Iodoanisole and p-iodotoluene, which bear electron-donating substituents, gave the corresponding nitriles 2c and 2d in yields of 45 and 42%, respectively. p-Iodoacetophenone and ethyl 4-iodobenzoate, which bear electron-withdrawing groups, gave the corresponding nitriles 2e and 2f in yields of 25 and 20%, respectively. In contrast, 4-iodobiphenyl, a π-extended precursor, gave nitrile 2g in 62% yield. The dicyanated product 2h was readily obtained from 4,4′-diiodobiphenyl.
To obtain further insights into the reaction mechanism, we conducted two control experiments (Scheme [3]). When the cyanation was carried out in DMSO-d 6, nitrile 2a was obtained in 63% yield together with deuterated naphthalene 3a-d (58% D) [Scheme [3](a)]. This result suggests that the major hydrogen donor of the reaction is DMSO, although there are other hydrogen sources.[11] When the reaction was carried out in the presence of 20 mol% of TEMPO, the cyanation did not proceed at all [Scheme [3](b)]. Even with 5 mol % of TEMPO, only a trace of 2a was obtained and a quantitative amount of 1a was recovered. These results suggest that the reaction proceeds via radical intermediates.[12]
A plausible mechanism for the phen-promoted cyanation reaction is shown in Scheme [4]. First, SET occurs to the aryl iodide 1 from phen, which has a more-positive reduction potential than that of 1 (see SI); this generates a radical anion of the aryl iodide A. Subsequent elimination of iodide (I−) gives aryl radical B, which reacts with DMSO to give the dehalogenated product ArH. When B reacts with –CN, an aryl cyanide radical anion C is generated. Subsequent SET from C to 1 affords the aryl cyanide 2 with regeneration of A.
As mentioned above, the cyanation reaction proceeded in the presence of a catalytic amount of phen, meaning that phen operates as a SET initiator in the first stage of the reaction to generate the radical anion A. We therefore examined the use of electroreduction instead of phen to generate the initial radical anion species (Scheme [5]). Electricity was simply passed through a mixed solution of the aryl iodide 1a and Et4NCN (5.0 equiv) in DMSO at 70 °C. With 0.3 F of electricity per mole of iodide 1a, the iodide 1a was consumed and nitrile 2a was obtained in 68% yield. Notably, the reaction proceeded with a catalytic amount of electricity. This result suggests that electricity is required for the generation of the aryl radical species and that the subsequent catalytic cycle proceeds without electricity in the same manner as the phen-promoted reaction. This protocol without any chemical initiator is operationally simple. In addition, it is advantageous that the reactions using electricity can be carried out at lower temperatures than those required for the phen-promoted reactions. Heating of the electrochemical reaction is mainly required because of the low solubility of Et4NCN in DMSO. Indeed, the electrochemical cyanation with Bu4NCN, which is more soluble than Et4NCN in DMSO, could be conducted at room temperature, and the desired product 2a was obtained in 60% yield. The high temperature necessary for the phen-promoted reaction might be due to the higher energy requirement for the SET from phen to the aryl iodide. In electrochemical reaction, electron-deficient aryl iodides gave better results than did electron-rich aryl iodides, probably because electron-deficient aryl iodides are more readily reduced to generate the corresponding aryl radical species. For instance, the electrochemical reaction of 4-iodoanisole did not give the desired compound 2c, whereas that of 3-iodoanisole gave the desired compound 2i in 24% yield. In contrast, the reaction of the electron-deficient aryl iodides p-iodoacetophenone, ethyl 4-iodobenzoate, and 4-iodobenzonitrile gave the desired products 2e, 2f, and 2j in yields of 68, 70, and 57%, respectively.
In conclusion, we have developed a phen-promoted cyanation reaction of aryl iodides with Et4NCN. Several aryl cyanides were synthesized by this method.[13] An electrochemical approach was also successful, and the cyanated products were obtained with a catalytic amount of electricity. Further investigations on the phen-promoted and electrochemical reactions are ongoing in our laboratory.
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Supporting Information
- Supporting information for this article is available online at https://doi-org.accesdistant.sorbonne-universite.fr/10.1055/s-0037-1611793.
- Supporting Information
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References and Notes
- 1a Kleemann A, Engel J, Kutscher B, Reichert D. Pharmaceutical Substances: Syntheses Patents, Applications, 4th ed. Thieme; Stuttgart: 2001
- 1b Larock RC. Comprehensive Organic Transformations: A Guide to Functional Group Preparations. Wiley-VCH; Weinheim: 1989: 819
- 1c Fleming FF, Yao L, Ravikumar PC, Funk L, Shook BC. J. Med. Chem. 2010; 53: 7902
- 2a Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 1633
- 2b Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 2650
- 2c Sandmeyer T. Ber. Dtsch. Chem. Ges. 1885; 18: 1492
- 2d Sandmeyer T. Ber. Dtsch. Chem. Ges. 1885; 18: 1496
- 2e Mo F, Qiu D, Zhang Y, Wang J. Acc. Chem. Res. 2018; 51: 496
- 3a Rosenmund KW, Struck E. Ber. Dtsch. Chem. Ges. 1919; 52: 1749
- 3b Koelsch CF, Whitney AG. J. Org. Chem. 1941; 6: 795
- 3c von Braun J, Manz G. Liebigs Ann. Chem. 1931; 488: 111
- 3d Connor JA, Leeming SW, Price R. J. Chem. Soc., Perkin Trans. 1 1990; 1127
- 3e Callen JE, Dornfeld CA, Coleman GH. Org. Synth. 1948; 28: 34
- 3f Wu JX, Beck B, Ren RX. Tetrahedron Lett. 2002; 43: 387
- 4a Anbarasan P, Schareina T, Beller M. Chem. Soc. Rev. 2011; 40: 5049
- 4b Sundermeier M, Zapf A, Beller M. Eur. J. Inorg. Chem. 2003; 3513
- 4c Yan G, Zhang Y, Wang J. Adv. Synth. Catal. 2017; 359: 4068
- 4d Kim J, Kim HJ, Chang S. Angew. Chem. Int. Ed. 2012; 51: 11948
- 4e Wang T, Jiao N. Acc. Chem. Res. 2014; 47: 1137
- 4f Ping Y, Ding Q, Peng Y. ACS Catal. 2016; 6: 5989
- 5a Zhang S, Neumann H, Beller M. Chem. Eur. J. 2018; 24: 67
- 5b Xia A, Xie X, Chen H, Zhao J, Zhang C, Liu Y. Org. Lett. 2018; 20: 7735
- 5c Makaravage KJ, Shao X, Brooks AF, Yang L, Sanford MS, Scott PJ. H. Org. Lett. 2018; 20: 1530
- 5d Gan Y, Wang G, Xie X, Liu Y. J. Org. Chem. 2018; 83: 14036
- 5e Zhang X, Xia A, Chen H, Liu Y. Org. Lett. 2017; 19: 2118
- 5f Kristensen SK, Eikeland EZ, Taarning E, Lindhardt AT, Skrydstrup T. Chem. Sci. 2017; 8: 8094
- 5g Kim K, Hong SH. Adv. Synth. Catal. 2017; 359: 2345
- 5h Coombs JR, Fraunhoffer KJ, Simmons EM, Stevens JM, Wisniewski SR, Yu M. J. Org. Chem. 2017; 82: 7040
- 5i Bag S, Jayarajan R, Dutta U, Chowdhury R, Mondal R, Maiti D. Angew. Chem. Int. Ed. 2017; 56: 12538
- 5j Škoch K, Císařová I, Štěpnička P. Organometallics 2015; 34: 1942
- 5k Sharif M, Wu X.-F. RSC Adv. 2015; 5: 21001
- 5l Nasrollahzadeh M, Jaleh B, Fakhri P, Zahraei A, Ghadery E. RSC Adv. 2015; 5: 2785
- 5m Mishra NK, Jeong T, Sharma S, Shin Y, Han S, Park J, Oh JS, Kwak JH, Jung YH, Kim IS. Adv. Synth. Catal. 2015; 357: 1293
- 5n Cohen DT, Buchwald SL. Org. Lett. 2015; 17: 202
- 5o Zanon J, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 2890
- 6a Zheng S, Yu C, Shen Z. Org. Lett. 2012; 14: 3644
- 6b Shu Z, Ji W, Wang X, Zhou Y, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2014; 53: 2186
- 6c Dong J, Wu Z, Liu Z, Liu P, Sun P. J. Org. Chem. 2015; 80: 12588
- 6d Mishra NK, Jeong T, Sharma S, Shin Y, Han S, Park J, Oh JS, Kwak JH, Jung YH, Kim IS. Adv. Synth. Catal. 2015; 357: 1293
- 6e Okamoto K, Sakata N, Ohe K. Org. Lett. 2015; 17: 4670
- 6f Pawar AB, Chang S. Org. Lett. 2015; 17: 660
- 6g Zhao M, Zhang W, Shen Z. J. Org. Chem. 2015; 80: 8868
- 6h Zhu Y, Li L, Shen Z. Chem. Eur. J. 2015; 21: 13246
- 6i Zhu Y, Zhao M, Lu W, Li L, Shen Z. Org. Lett. 2015; 17: 2602
- 6j Liu W, Richter SC, Mei R, Feldt M, Ackermann L. Chem. Eur. J. 2016; 22: 17958
- 6k Takise R, Itami K, Yamaguchi J. Org. Lett. 2016; 18: 4428
- 6l Ogiwara Y, Morishita H, Sasaki M, Imai H, Sakai N. Chem. Lett. 2017; 46: 1736
- 6m Yan Y, Sun S, Cheng J. J. Org. Chem. 2017; 82: 12888
- 6n Yu P, Morandi B. Angew. Chem. Int. Ed. 2017; 56: 15693
- 6o Lv S, Li Y, Yao T, Yu X, Zhang C, Hai L, Wu Y. Org. Lett. 2018; 20: 4994
- 6p Shirsath SR, Shinde GH, Shaikh AC, Muthukrishnan M. J. Org. Chem. 2018; 83: 12305
- 6q Yu X, Tang J, Jin X, Yamamoto Y, Bao M. Asian J. Org. Chem. 2018; 7: 550
- 6r Ueda Y, Tsujimoto N, Yurino T, Tsurugi H, Mashima K. Chem. Sci. 2019; 10: 994
- 7a Dohi T, Morimoto K, Kiyono Y, Tohma H, Kita Y. Org. Lett. 2005; 7: 537
- 7b Dohi T, Morimoto K, Takenaga N, Goto A, Maruyama A, Kiyono Y, Tohma H, Kita Y. J. Org. Chem. 2007; 72: 109
- 7c Yang Y, Zhang Y, Wang J. Org. Lett. 2011; 13: 5608
- 7d McManus J, Nicewicz D. J. Am. Chem. Soc. 2017; 139: 2880
- 8a Petrillo G, Novi M, Garbarino G, Dell’erba C. Tetrahedron 1987; 43: 4625
- 8b Novi M, Garbarino G, Petrillo G, Dell’erba C. Tetrahedron 1990; 46: 2205
- 9a Yanagisawa S, Ueda K, Taniguchi T, Itami K. Org. Lett. 2008; 10: 4673
- 9b Sun C.-L, Li H, Yu D.-G, Yu M, Zhou X, Lu X.-Y, Huang K, Zheng S.-F, Li B.-J, Shi Z.-J. Nat. Chem. 2010; 2: 1044
- 9c Shirakawa E, Itoh K.-i, Higashino T, Hayashi T. J. Am. Chem. Soc. 2010; 132: 15537
- 9d Liu W, Cao H, Zhang H, Zhang H, Chung KH, He C, Wang H, Kwong FY, Lei A. J. Am. Chem. Soc. 2010; 132: 16737
- 9e Qiu Y, Liu Y, Yang K, Hong W, Li Z, Wang Z, Yao Z, Jiang S. Org. Lett. 2011; 13: 3556
- 9f Budén ME, Guastavino JF, Rossi RA. Org. Lett. 2013; 15: 1174
- 9g Dewanji A, Murarka S, Curran DP, Studer A. Org. Lett. 2013; 15: 6102
- 9h Leifert D, Daniliuc CG, Studer A. Org. Lett. 2013; 15: 6286
- 9i Wertz S, Leifert D, Studer A. Org. Lett. 2013; 15: 928
- 9j Song Q, Zhang D, Zhu Q, Xu Y. Org. Lett. 2014; 16: 5272
- 9k Studer A, Curran DP. Nat. Chem. 2014; 6: 765
- 9l Hartmann M, Daniliuc CG, Studer A. Chem. Commun. 2015; 51: 3121
- 9m Leifert D, Studer A. Org. Lett. 2015; 17: 386
- 9n Anton-Torrecillas C, Felipe-Blanco D, Gonzalez-Gomez JC. Org. Biomol. Chem. 2016; 14: 10620
- 9o Jia F.-C, Xu C, Zhou Z.-W, Cai Q, Wu Y.-D, Wu A.-X. Org. Lett. 2016; 18: 5232
- 9p Zhang L, Yang H, Jiao L. J. Am. Chem. Soc. 2016; 138: 7151
- 9q Budén ME, Bardagi JI, Puiatti M, Rossi RA. J. Org. Chem. 2017; 82: 8325
- 9r Taniguchi T, Naka T, Imoto M, Takeda M, Nakai T, Mihara M, Mizuno T, Nomoto A, Ogawa A. J. Org. Chem. 2017; 82: 6647
- 9s Barham JP, Dalton SE, Allison M, Nocera G, Young A, John MP, McGuire T, Campos S, Tuttle T, Murphy JA. J. Am. Chem. Soc. 2018; 140: 11510
- 9t Guo Z, Li M, Mou X.-Q, He G, Xue X.-S, Chen G. Org. Lett. 2018; 20: 1684
- 9u Shirakawa E, Hayashi T. Chem. Lett. 2012; 41: 130
- 9v Shirakawa E, Watabe R, Murakami T, Hayashi T. Chem. Commun. 2013; 49: 5219
- 9w Shirakawa E, Tamakuni F, Kusano E, Uchiyama N, Konagaya W, Watabe R, Hayashi T. Angew. Chem. Int. Ed. 2014; 53: 521
- 9x Ueno R, Ikeda Y, Shirakawa E. Eur. J. Org. Chem. 2017; 2017: 4188
- 9y Ikeda Y, Ueno R, Akai Y, Shirakawa E. Chem. Commun. 2018; 54: 10471
- 9z Kiriyama K, Okura K, Tamakuni F, Shirakawa E. Chem. Eur. J. 2018; 24: 4519
- 9aa Okura K, Teranishi T, Yoshida Y, Shirakawa E. Angew. Chem. Int. Ed. 2018; 57: 7186
- 10 Shirakawa and Hayashi reported that their cross-coupling reaction did not proceed without t -BuOM [see Ref. 9(c)].
- 11 Caminos DA, Garro AD, Soria-Castro SM, Alicia B, Peñéñory AB. RSC Adv. 2015; 5: 20058
- 12 It is known that the addition of TEMPO suppresses SRN1-type reactions; see refs 9(a), 9(d), and 9(e).
- 13 1-Naphthonitrile (2a); Typical ProcedureA solution of 1-iodonaphthalene (127 mg, 0.50 mmol), Et4NCN (391 mg, 2.50 mmol), and 1,10-phenanthroline (18.2 mg, 0.1 mmol) in DMSO (1 mL) was stirred at 130 °C for 1 h. H2O (15 mL) was added and the resulting mixture was extracted with EtOAc (3 × 5 mL). The combined organic phase was dried (MgSO4), filtered, and concentrated under reduced pressure. The residue was purified by column chromatography [silica gel, hexane–EtOAc (30:1)] to give a yellow oil; yield: 59.5 mg (0.39 mmol, 78%).IR (neat): 3061, 2222, 1591, 1512, 1375 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.53 (t, J = 7.8 Hz, 1 H), 7.63 (t, J = 7.6 Hz, 1 H), 7.70 (t, J = 7.9 Hz, 1 H), 7.87–7.96 (m, 2 H), 8.08 (d, J = 7.9 Hz, 1 H), 8.24 (d, J = 7.9 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 110.0, 117.7, 124.8, 125.0, 127.4, 128.5, 128.6, 132.2, 132.5, 132.8, 133.2.
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References and Notes
- 1a Kleemann A, Engel J, Kutscher B, Reichert D. Pharmaceutical Substances: Syntheses Patents, Applications, 4th ed. Thieme; Stuttgart: 2001
- 1b Larock RC. Comprehensive Organic Transformations: A Guide to Functional Group Preparations. Wiley-VCH; Weinheim: 1989: 819
- 1c Fleming FF, Yao L, Ravikumar PC, Funk L, Shook BC. J. Med. Chem. 2010; 53: 7902
- 2a Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 1633
- 2b Sandmeyer T. Ber. Dtsch. Chem. Ges. 1884; 17: 2650
- 2c Sandmeyer T. Ber. Dtsch. Chem. Ges. 1885; 18: 1492
- 2d Sandmeyer T. Ber. Dtsch. Chem. Ges. 1885; 18: 1496
- 2e Mo F, Qiu D, Zhang Y, Wang J. Acc. Chem. Res. 2018; 51: 496
- 3a Rosenmund KW, Struck E. Ber. Dtsch. Chem. Ges. 1919; 52: 1749
- 3b Koelsch CF, Whitney AG. J. Org. Chem. 1941; 6: 795
- 3c von Braun J, Manz G. Liebigs Ann. Chem. 1931; 488: 111
- 3d Connor JA, Leeming SW, Price R. J. Chem. Soc., Perkin Trans. 1 1990; 1127
- 3e Callen JE, Dornfeld CA, Coleman GH. Org. Synth. 1948; 28: 34
- 3f Wu JX, Beck B, Ren RX. Tetrahedron Lett. 2002; 43: 387
- 4a Anbarasan P, Schareina T, Beller M. Chem. Soc. Rev. 2011; 40: 5049
- 4b Sundermeier M, Zapf A, Beller M. Eur. J. Inorg. Chem. 2003; 3513
- 4c Yan G, Zhang Y, Wang J. Adv. Synth. Catal. 2017; 359: 4068
- 4d Kim J, Kim HJ, Chang S. Angew. Chem. Int. Ed. 2012; 51: 11948
- 4e Wang T, Jiao N. Acc. Chem. Res. 2014; 47: 1137
- 4f Ping Y, Ding Q, Peng Y. ACS Catal. 2016; 6: 5989
- 5a Zhang S, Neumann H, Beller M. Chem. Eur. J. 2018; 24: 67
- 5b Xia A, Xie X, Chen H, Zhao J, Zhang C, Liu Y. Org. Lett. 2018; 20: 7735
- 5c Makaravage KJ, Shao X, Brooks AF, Yang L, Sanford MS, Scott PJ. H. Org. Lett. 2018; 20: 1530
- 5d Gan Y, Wang G, Xie X, Liu Y. J. Org. Chem. 2018; 83: 14036
- 5e Zhang X, Xia A, Chen H, Liu Y. Org. Lett. 2017; 19: 2118
- 5f Kristensen SK, Eikeland EZ, Taarning E, Lindhardt AT, Skrydstrup T. Chem. Sci. 2017; 8: 8094
- 5g Kim K, Hong SH. Adv. Synth. Catal. 2017; 359: 2345
- 5h Coombs JR, Fraunhoffer KJ, Simmons EM, Stevens JM, Wisniewski SR, Yu M. J. Org. Chem. 2017; 82: 7040
- 5i Bag S, Jayarajan R, Dutta U, Chowdhury R, Mondal R, Maiti D. Angew. Chem. Int. Ed. 2017; 56: 12538
- 5j Škoch K, Císařová I, Štěpnička P. Organometallics 2015; 34: 1942
- 5k Sharif M, Wu X.-F. RSC Adv. 2015; 5: 21001
- 5l Nasrollahzadeh M, Jaleh B, Fakhri P, Zahraei A, Ghadery E. RSC Adv. 2015; 5: 2785
- 5m Mishra NK, Jeong T, Sharma S, Shin Y, Han S, Park J, Oh JS, Kwak JH, Jung YH, Kim IS. Adv. Synth. Catal. 2015; 357: 1293
- 5n Cohen DT, Buchwald SL. Org. Lett. 2015; 17: 202
- 5o Zanon J, Klapars A, Buchwald SL. J. Am. Chem. Soc. 2003; 125: 2890
- 6a Zheng S, Yu C, Shen Z. Org. Lett. 2012; 14: 3644
- 6b Shu Z, Ji W, Wang X, Zhou Y, Zhang Y, Wang J. Angew. Chem. Int. Ed. 2014; 53: 2186
- 6c Dong J, Wu Z, Liu Z, Liu P, Sun P. J. Org. Chem. 2015; 80: 12588
- 6d Mishra NK, Jeong T, Sharma S, Shin Y, Han S, Park J, Oh JS, Kwak JH, Jung YH, Kim IS. Adv. Synth. Catal. 2015; 357: 1293
- 6e Okamoto K, Sakata N, Ohe K. Org. Lett. 2015; 17: 4670
- 6f Pawar AB, Chang S. Org. Lett. 2015; 17: 660
- 6g Zhao M, Zhang W, Shen Z. J. Org. Chem. 2015; 80: 8868
- 6h Zhu Y, Li L, Shen Z. Chem. Eur. J. 2015; 21: 13246
- 6i Zhu Y, Zhao M, Lu W, Li L, Shen Z. Org. Lett. 2015; 17: 2602
- 6j Liu W, Richter SC, Mei R, Feldt M, Ackermann L. Chem. Eur. J. 2016; 22: 17958
- 6k Takise R, Itami K, Yamaguchi J. Org. Lett. 2016; 18: 4428
- 6l Ogiwara Y, Morishita H, Sasaki M, Imai H, Sakai N. Chem. Lett. 2017; 46: 1736
- 6m Yan Y, Sun S, Cheng J. J. Org. Chem. 2017; 82: 12888
- 6n Yu P, Morandi B. Angew. Chem. Int. Ed. 2017; 56: 15693
- 6o Lv S, Li Y, Yao T, Yu X, Zhang C, Hai L, Wu Y. Org. Lett. 2018; 20: 4994
- 6p Shirsath SR, Shinde GH, Shaikh AC, Muthukrishnan M. J. Org. Chem. 2018; 83: 12305
- 6q Yu X, Tang J, Jin X, Yamamoto Y, Bao M. Asian J. Org. Chem. 2018; 7: 550
- 6r Ueda Y, Tsujimoto N, Yurino T, Tsurugi H, Mashima K. Chem. Sci. 2019; 10: 994
- 7a Dohi T, Morimoto K, Kiyono Y, Tohma H, Kita Y. Org. Lett. 2005; 7: 537
- 7b Dohi T, Morimoto K, Takenaga N, Goto A, Maruyama A, Kiyono Y, Tohma H, Kita Y. J. Org. Chem. 2007; 72: 109
- 7c Yang Y, Zhang Y, Wang J. Org. Lett. 2011; 13: 5608
- 7d McManus J, Nicewicz D. J. Am. Chem. Soc. 2017; 139: 2880
- 8a Petrillo G, Novi M, Garbarino G, Dell’erba C. Tetrahedron 1987; 43: 4625
- 8b Novi M, Garbarino G, Petrillo G, Dell’erba C. Tetrahedron 1990; 46: 2205
- 9a Yanagisawa S, Ueda K, Taniguchi T, Itami K. Org. Lett. 2008; 10: 4673
- 9b Sun C.-L, Li H, Yu D.-G, Yu M, Zhou X, Lu X.-Y, Huang K, Zheng S.-F, Li B.-J, Shi Z.-J. Nat. Chem. 2010; 2: 1044
- 9c Shirakawa E, Itoh K.-i, Higashino T, Hayashi T. J. Am. Chem. Soc. 2010; 132: 15537
- 9d Liu W, Cao H, Zhang H, Zhang H, Chung KH, He C, Wang H, Kwong FY, Lei A. J. Am. Chem. Soc. 2010; 132: 16737
- 9e Qiu Y, Liu Y, Yang K, Hong W, Li Z, Wang Z, Yao Z, Jiang S. Org. Lett. 2011; 13: 3556
- 9f Budén ME, Guastavino JF, Rossi RA. Org. Lett. 2013; 15: 1174
- 9g Dewanji A, Murarka S, Curran DP, Studer A. Org. Lett. 2013; 15: 6102
- 9h Leifert D, Daniliuc CG, Studer A. Org. Lett. 2013; 15: 6286
- 9i Wertz S, Leifert D, Studer A. Org. Lett. 2013; 15: 928
- 9j Song Q, Zhang D, Zhu Q, Xu Y. Org. Lett. 2014; 16: 5272
- 9k Studer A, Curran DP. Nat. Chem. 2014; 6: 765
- 9l Hartmann M, Daniliuc CG, Studer A. Chem. Commun. 2015; 51: 3121
- 9m Leifert D, Studer A. Org. Lett. 2015; 17: 386
- 9n Anton-Torrecillas C, Felipe-Blanco D, Gonzalez-Gomez JC. Org. Biomol. Chem. 2016; 14: 10620
- 9o Jia F.-C, Xu C, Zhou Z.-W, Cai Q, Wu Y.-D, Wu A.-X. Org. Lett. 2016; 18: 5232
- 9p Zhang L, Yang H, Jiao L. J. Am. Chem. Soc. 2016; 138: 7151
- 9q Budén ME, Bardagi JI, Puiatti M, Rossi RA. J. Org. Chem. 2017; 82: 8325
- 9r Taniguchi T, Naka T, Imoto M, Takeda M, Nakai T, Mihara M, Mizuno T, Nomoto A, Ogawa A. J. Org. Chem. 2017; 82: 6647
- 9s Barham JP, Dalton SE, Allison M, Nocera G, Young A, John MP, McGuire T, Campos S, Tuttle T, Murphy JA. J. Am. Chem. Soc. 2018; 140: 11510
- 9t Guo Z, Li M, Mou X.-Q, He G, Xue X.-S, Chen G. Org. Lett. 2018; 20: 1684
- 9u Shirakawa E, Hayashi T. Chem. Lett. 2012; 41: 130
- 9v Shirakawa E, Watabe R, Murakami T, Hayashi T. Chem. Commun. 2013; 49: 5219
- 9w Shirakawa E, Tamakuni F, Kusano E, Uchiyama N, Konagaya W, Watabe R, Hayashi T. Angew. Chem. Int. Ed. 2014; 53: 521
- 9x Ueno R, Ikeda Y, Shirakawa E. Eur. J. Org. Chem. 2017; 2017: 4188
- 9y Ikeda Y, Ueno R, Akai Y, Shirakawa E. Chem. Commun. 2018; 54: 10471
- 9z Kiriyama K, Okura K, Tamakuni F, Shirakawa E. Chem. Eur. J. 2018; 24: 4519
- 9aa Okura K, Teranishi T, Yoshida Y, Shirakawa E. Angew. Chem. Int. Ed. 2018; 57: 7186
- 10 Shirakawa and Hayashi reported that their cross-coupling reaction did not proceed without t -BuOM [see Ref. 9(c)].
- 11 Caminos DA, Garro AD, Soria-Castro SM, Alicia B, Peñéñory AB. RSC Adv. 2015; 5: 20058
- 12 It is known that the addition of TEMPO suppresses SRN1-type reactions; see refs 9(a), 9(d), and 9(e).
- 13 1-Naphthonitrile (2a); Typical ProcedureA solution of 1-iodonaphthalene (127 mg, 0.50 mmol), Et4NCN (391 mg, 2.50 mmol), and 1,10-phenanthroline (18.2 mg, 0.1 mmol) in DMSO (1 mL) was stirred at 130 °C for 1 h. H2O (15 mL) was added and the resulting mixture was extracted with EtOAc (3 × 5 mL). The combined organic phase was dried (MgSO4), filtered, and concentrated under reduced pressure. The residue was purified by column chromatography [silica gel, hexane–EtOAc (30:1)] to give a yellow oil; yield: 59.5 mg (0.39 mmol, 78%).IR (neat): 3061, 2222, 1591, 1512, 1375 cm–1. 1H NMR (400 MHz, CDCl3): δ = 7.53 (t, J = 7.8 Hz, 1 H), 7.63 (t, J = 7.6 Hz, 1 H), 7.70 (t, J = 7.9 Hz, 1 H), 7.87–7.96 (m, 2 H), 8.08 (d, J = 7.9 Hz, 1 H), 8.24 (d, J = 7.9 Hz, 1 H). 13C NMR (100 MHz, CDCl3): δ = 110.0, 117.7, 124.8, 125.0, 127.4, 128.5, 128.6, 132.2, 132.5, 132.8, 133.2.
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