Indium(III)-Catalyzed One-Pot Synthesis of Alkyl Cyanides from Carboxylic Acids

Abstract

The one-pot preparation of alkyl cyanides from carboxylic acids via alkyl iodides or alkyl bromides, which were in situ generated either by indium(III)-catalyzed reductive iodination or bromination of carboxylic acids, is described.

Key words

indium - deoxygenation - halogenation - carboxylic ­acids - nitriles

• References

• 1 The Chemistry of the Cyano Group . Rappoport Z. Wiley-Interscience; London: 1970

For some recent examples of functional transformations of cyanides, see:
• 2a Addis D, Enthaler S, Junge K, Wendt B, Beller M. Tetrahedron Lett. 2009; 50: 3654
• 2b Enthaler S, Addis D, Junge K, Erre G, Beller M. Chem. Eur. J. 2008; 14: 9491
• 2c Saavedra JZ, Resemdez A, Rovira A, Eagon S, Haddenham D, Singaram BJ. J. Org. Chem. 2012; 77: 221
• 2d Lee W.-C, Sears JM, Enow RA, Eads K, Krogstad DA, Frost BJ. Inorg. Chem. 2013; 52: 1737
• 3 Furukawa N, Kishimoto K, Ogawa S, Kawai T, Fujihara H, Oae S. Tetrahedron Lett. 1981; 22: 4409
• 4 For recent examples on the reactions using Me₃SiCN, see: Soleimani E. Synlett 2007; 1625 ; and references cited therein
• 5 Chen G, Wang Z, Wu J, Ding K. Org. Lett. 2008; 10: 4573
• 6 Bandini M, Cozzi GP, Giacomini M, Melchiorre P, Selva S, Umani-Ronchi AJ. J. Org. Chem. 2002; 67: 3700
• 7a Sakai N, Moriya T, Konakahara T. J. Org. Chem. 2007; 72: 5920
• 7b Sakai N, Fujii K, Konakahara T. Tetrahedron Lett. 2008; 49: 6873
• 7c Sakai N, Moriya T, Fujii K, Konakahara T. Synthesis 2008; 3533
• 7d Sakai N, Nagasawa K, Ikeda R, Nakaike Y, Konakahara T. Tetrahedron Lett. 2011; 52: 3133
• 7e Sakai N, Usui Y, Ikeda R, Konakahara T. Adv. Synth. Catal. 2011; 353: 3397
• 7f Sakai N, Kawana K, Ikeda R, Nakaike Y, Konakahara T. Eur. J. Org. Chem. 2011; 3178
• 7g Sakai N, Usui Y, Moriya T, Ikeda R, Konakahara T. Eur. J. Org. Chem. 2012; 4603
• 8 Bromination of carboxylic acids with this reducing system was already communicated, see: Moriya T, Yoneda S, Kawana K, Ikeda R, Konakahara T, Sakai N. Org. Lett. 2012; 14: 4842
• 9 Hypervalent trimethylfluorocyanosilicate [Me₃SiFCN]^–Bu₄N⁺ was generated from Me₃SiCN (1 equiv) and TBAF (1 equiv) in situ and used without further purification. For the preparation of cyanosilicate, see: Soli DE, Manoso SA, Patterson CM, DeShong P. J. Org. Chem. 1999; 64: 3171
• 10 The reactivity and handling of the cyanation by either method A or method B were almost equivalent. However, in several cases, method A produced unidentified by-products, which precluded isolating the desired alkyl cyanides.
• 11 When benzyl bromide was treated with a mixture of TBAF and Me₃SiCN in the absence of both InBr₃ and TMDS, the corresponding cyanation product was obtained in good yield.
• 12 It seemed that due to the decomposition of the phenylthio moiety, the yield of the product was low. Practically, the prolonged reaction time led to decomposition preventing the isolation of the product 3m.
• 13 Chiba S, Zhang L, Ang YG, Hui WB. Org. Lett. 2010; 12: 2052
• 14 Suzuki Y, Yoshino T, Moriyama K, Togo H. Tetrahedron 2011; 67: 3809
• 15 Nador F, Moglie Y, Vitale C, Yus M, Alonso F, Radivoy G. Tetrahedron 2010; 66: 4318
• 16 Gardner RA, Delcros J.-G, Konate F, Breitbeil III F, Martin B, Sigman M, Huang M, Phanstiel OIV. J. Med. Chem. 2004; 47: 6055
• 17 Black PJ, Edwards MG, Williams MJ. Eur. J. Org. Chem. 2006; 4367
• 18 Dong C.-Z, Ahamada-Himidi A, Plocki S, Aoun D, Touaibia M, Habich M.-B, Huet J, Redeuilh C, Ombeta JE, Godfroid J.-J, Massicot F, Heymans F. Bioorg. Med. Chem. 2005; 13: 1989
• 19 Velcicky J, Soicke A, Steiner R, Schmalz HG. J. Am. Chem. Soc. 2011; 133: 6948
• 20 Lenardao EJ, Trecha DO, Ferreira PC, Jacob RG, Perin G. J. Braz. Chem. Soc. 2009; 20: 93 ; Chem. Abstr. 2009, 151, 288540
• 21 Bradamante S, Pagani GA. J. Org. Chem. 1980; 45: 114