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Synthesis 2014; 46(20): 2747-2750
DOI: 10.1055/s-0034-1378322
DOI: 10.1055/s-0034-1378322
paper
Copper-Catalyzed Regioselective Allylic Cyanation of Allylic Compounds with Trimethylsilyl Cyanide
Further Information
Publication History
Received: 25 April 2014
Accepted after revision: 23 May 2014
Publication Date:
09 July 2014 (online)
Abstract
The copper-catalyzed regioselective allylic cyanation of allylic compounds with trimethylsilyl cyanide (TMSCN) is described. Copper(I) iodide (CuI), copper(I) cyanide (CuCN) and copper(II) chloride (CuCl2) are shown to effectively catalyze the cyanation of various allylic substrates to afford the corresponding allylic cyanides in good yields and high regioselectivities. The reaction in the presence of 2,2,6,6-tetramethyl-1-piperidinyloxy free radical (TEMPO) reveals that the cyanation proceeds via a radical pathway.
Supporting Information
- for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000084.
- Supporting Information
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References
- 1a Hartwig JF. Organotransition Metal Chemistry: From Bonding to Catalysis. University Science Books; Sausalito: 2010: 967-1014
- 1b Tsuji J. Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis. John Wiley & Sons; Chichester: 2000: 109-168
- 1c Lu Z, Ma S. Angew. Chem. Int. Ed. 2008; 47: 258
- 2a Reetz MT, Chatziiosifidis I, Künzer H, Müller-Starke H. Tetrahedron 1983; 39: 961
- 2b Miyake H, Yamamura K. Tetrahedron Lett. 1986; 27: 3025
- 2c Murakami M, Kato T, Mukaiyama T. Chem. Lett. 1987; 1167
- 2d Hayashi Y, Mukaiyama T. Chem. Lett. 1987; 1811
- 2e Tsuji Y, Taniguchi M, Yasuda T, Kawamura T, Obora Y. Org. Lett. 2000; 2: 2635
- 2f Singh V, Pathak R, Batra S. Catal. Commun. 2007; 8: 2048
- 2g Chen G, Wang Z, Wu J, Ding K. Org. Lett. 2008; 10: 4573
- 2h Wang J, Masui Y, Onaka M. ACS Catal. 2011; 1: 446
- 2i He Y.-T, Li L.-H, Yang Y.-F, Zhou Z.-Z, Hus H.-L, Liu X.-Y, Liang Y.-M. Org. Lett. 2014; 16: 270
-
3a Tsuji Y, Yamada N, Tanaka S. J. Org. Chem. 1993; 58: 16
- 3b Tsuji Y, Kusui T, Kojima T, Sugiura Y, Yamada N, Tanaka S, Ebihara M, Kawamura T. Organometallics 1998; 17: 4835
- 4a Alexakis A, Bäckvall JE, Krause N, Pàmies O, Diéguez M. Chem. Rev. 2008; 108: 2796
-
4b Harutyunyan SR, den Hartog T, Geurts K, Minnaard AJ, Feringa BL. Chem. Rev. 2008; 108: 2824
- 4c Yorimitsu H, Oshima K. Angew. Chem. Int. Ed. 2005; 44: 4435
- 4d Wen Q, Jin J, Zhang L, Luo Y, Lu P, Wang Y. Tetrahedron Lett. 2014; 55: 1271
- 5a Karlström AS. E, Bäckvall J.-E. Chem. Eur. J. 2001; 7: 1981
- 5b Ito H, Kawakami C, Sawamura M. J. Am. Chem. Soc. 2005; 127: 16034
- 5c Ito H, Ito S, Sasaki Y, Matsuura K, Sawamura M. J. Am. Chem. Soc. 2007; 129: 14856
- 5d Bartholomew ER, Bertz SH, Cope S, Murphy M, Ogle CA. J. Am. Chem. Soc. 2008; 130: 11244
- 5e Yoshikai N, Zhang S.-L, Nakamura E. J. Am. Chem. Soc. 2008; 130: 12862
- 5f Ito H, Ito S, Sasaki Y, Matsuura K, Sawamura M. Pure Appl. Chem. 2008; 80: 1039
- 5g Ohmiya H, Yokokawa N, Sawamura M. Org. Lett. 2010; 12: 2438
- 5h Shintani R, Takatsu K, Takeda M, Hayashi T. Angew. Chem. Int. Ed. 2011; 50: 8656
- 5i Li D, Ohmiya H, Sawamura M. J. Am. Chem. Soc. 2011; 133: 5672
- 5j Miyake Y, Ota S.-i, Nishibayashi Y. Chem. Eur. J. 2012; 18: 13255
- 5k Li H, Alexakis A. Angew. Chem. Int. Ed. 2012; 51: 1055
- 5l Nagao K, Yokobori U, Makida Y, Ohmiya H, Sawamura M. J. Am. Chem. Soc. 2012; 134: 8982
- 5m Shido Y, Yoshida M, Tanabe M, Ohmiya H, Sawamura M. J. Am. Chem. Soc. 2012; 134: 18573
- 5n Makida Y, Ohmiya H, Sawamura M. Angew. Chem. Int. Ed. 2012; 51: 4122
- 5o Li D, Ohmiya H, Sawamura M. Synthesis 2012; 44: 1304
- 5p Makida Y, Takayama Y, Ohmiya H, Sawamura M. Angew. Chem. Int. Ed. 2013; 52: 5350
- 5q Hornillos V, Pérez M, Fañanás-Mastral M, Feringa BL. Chem. Eur. J. 2013; 19: 5432
- 5r Sheng W, Wang M, Lein M, Jiang L, Wei W, Wang J. Chem. Eur. J. 2013; 19: 14126
- 6 We also found that the reactions of substrates 10a and 10b with NaCN resulted in no reaction at 80 °C in MeCN.
- 7a Nishikata T, Noda Y, Fujimoto R, Sakashita T. J. Am. Chem. Soc. 2013; 135: 16372
- 7b Presset M, Oehlrich D, Rombouts F, Molander GA. J. Org. Chem. 2013; 78: 12837
- 7c Chu L, Qing F.-L. Org. Lett. 2012; 14: 2106
- 7d Wang X, Ye Y, Zhang S, Feng J, Xu Y, Zhang Y, Wang J. J. Am. Chem. Soc. 2011; 133: 16410
- 7e Parsons AT, Buchwald SL. Angew. Chem. Int. Ed. 2011; 50: 9120
- 7f Jakubowski W, Tsarevsky NV, Higashihara T, Faust R, Matyjaszewski K. Macromolecules 2008; 41: 2318
- 7g Celio H, Scheer KC, White JM. J. Am. Chem. Soc. 2001; 123: 2990
- 8a Lehmann J, Lloyd-Jones GC. Tetrahedron 1995; 51: 8863
-
8b Hoveyda HR, Vézina M. Org. Lett. 2005; 7: 2113
- 9a Kawatsura M, Uchida K, Terasaki S, Tsuji H, Minakawa M, Itoh T. Org. Lett. 2014; 16: 1470
- 9b Kawatsura M, Tsuji H, Uchida K, Itoh T. Tetrahedron 2011; 67: 7686
- 9c Kawatsura M, Ata F, Hayase S, Itoh T. Chem. Commun. 2007; 4283