Nickel-catalyzed hydrocyanation of non-activated C–C multiple bonds has been one of the most powerful cyanation protocols.1 Facile access to various carbonitriles through this transformation is very advantageous, however its regiocontrol, particularly using allenes, is still challenging.2 On the other hand, we found that hydrocyanation of 1,3-disubstituted aryl allene (1) gave 2 in high yield and selectivity with bench-stable Ni(0) species (Scheme 1).3 The key point of this transformation is regioselective C-H bond formation to give ally Ni complex (II) through π-allyl Ni complex (I). When optically active allene ((R)-1) was used, axial chirality was successfully transferred to sp3 stereogenic center (Scheme 2). The key point is site-, regio- and faceselective hydronickelation of one of four p-orbitals. References 1) Taylor, B. W.; Swift, H.-E. J. Catal. 1972, 26, 254.; 2) Sakakibara, Y.; Matsuzaka, S.; Nagamine, S.; Sakai, M.; Uchino, N. Nippon Kagaku Kaishi 1985, 409.; 3) Arai, S.; Hori, H.; Amako, Y.; Nishida A. Chem. Commun. 2015, 51, 7493.

Nickel-catalyzed regio- and stereoselective hydrocyanation of allene

251st National Meeting (2016)

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