Direct catalytic asymmetric addition of allyl cyanide to ketones.
A direct catalytic asymmetric addition of allyl cyanide to ketones with a bimetallic catalytic system comprising (R,R)-Ph-BPE/[Cu(CH(3)CN)(4)]ClO(4)/LiOAr is described. Exclusive gamma-addition of allyl cyanide was observed, affording optically enriched tertiary alcohols bearing Z-configured alpha,beta-unsaturated nitriles. The reaction proceeded under proton-transfer conditions, utilizing soft Lewis acid/hard Brønsted base bifunctional catalysis. The applicability of the reaction to aromatic, heteroaromatic, and aliphatic ketones demonstrates its wide substrate generality.
Yazaki
Ryo
R
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
Kumagai
Naoya
N
Shibasaki
Masakatsu
M
D002384:Catalysis; D003198:Computer Simulation; D007659:Ketones / Q000138:chemical synthesis* / Q000737:chemistry; D008956:Models, Chemical; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D013237:Stereoisomerism
D007659:Ketones; D009570:Nitriles