Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine

Yohei Ueda; Nagataka Tsujimoto; Taiga Yurino; Hayato Tsurugi; Kazushi Mashima

doi:10.1039/c8sc04437f

Nickel-catalyzed cyanation of aryl halides and triflates using acetonitrile via C-CN bond cleavage assisted by 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine

Chem Sci. 2018 Nov 26;10(4):994-999. doi: 10.1039/c8sc04437f. eCollection 2019 Jan 28.

Authors

Yohei Ueda¹, Nagataka Tsujimoto¹, Taiga Yurino¹, Hayato Tsurugi¹, Kazushi Mashima¹

Affiliation

¹ Department of Chemistry , Graduate School of Engineering Science , Osaka University , Toyonaka , Osaka 560-8531 , Japan . Email: tsurugi@chem.es.osaka-u.ac.jp ; Email: mashima@chem.es.osaka-u.ac.jp.

Abstract

We developed a non-toxic cyanation reaction of various aryl halides and triflates in acetonitrile using a catalyst system of [Ni(MeCN)₆](BF₄)₂, 1,10-phenanthroline, and 1,4-bis(trimethylsilyl)-2,3,5,6-tetramethyl-1,4-dihydropyrazine (Si-Me₄-DHP). Si-Me₄-DHP was found to function as a reductant for generating nickel(0) species and a silylation reagent to achieve the catalytic cyanation via C-CN bond cleavage.