title: Straightforward synthesis of 1,2-dicyanoalkanes from nitroalkenes and silyl cyanide mediated by tetrabutylammonium fluoride.
abstract: A straightforward synthesis of 1,2-dicyanoalkanes by reacting nitroalkenes with trimethylsilyl cyanide in the presence of tetrabutylammonium fluoride is described. The reaction proceeds through a tandem double Michael addition under mild conditions. Employing the hypervalent silicate generated from trimethylsilyl cyanide and tetrabutylammonium fluoride is essential for achieving this transformation. Mechanistic studies suggest that a small amount of water included in the reaction media plays a key role. This protocol is applicable to various types of substrates including electron-rich and electron-deficient aromatic nitroalkenes, and aliphatic nitroalkenes. Moreover, vinyl sulfones were found to be good alternatives, particularly for electron-deficient nitroalkenes. The broad substrate scope and functional group tolerance of the reaction makes this approach a practical method for the synthesis of valuable 1,2-dicyanoalkanes.
authors.affiliation: Department of Applied Chemistry, Graduate School of Engineering, Osaka University, Yamadaoka 2-1, Suita, Osaka 565-0871 (Japan), Fax: (+81) 6-6879-7402.
authors.forename: Kensuke
authors.initials: K
authors.lastname: Kiyokawa
authors.forename: Takaya
authors.initials: T
authors.lastname: Nagata
authors.forename: Junpei
authors.initials: J
authors.lastname: Hayakawa
authors.forename: Satoshi
authors.initials: S
authors.lastname: Minakata
keywords: Michael addition; cyanides; fluoride; reaction mechanism; synthetic methods