Direct catalytic asymmetric addition of allylic cyanides to ketoimines.
Direct catalytic asymmetric addition of allylic cyanides to N-diphenylphosphinoyl ketoimines with a bimetallic catalytic system comprising Ph-BPE/[Cu(CH3CN)4]ClO4/LiOAr is described. Intermediary alpha-adducts readily isomerized to afford synthetically useful alpha,beta-unsaturated nitriles bearing an optically active tetrasubstituted carbon. Applicability to aromatic, heteroaromatic, and aliphatic ketoimines exemplifies wide substrate generality. Transformation of the product into densely functionalized material showcases the utility of the present protocol.
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Ryo
R
Yazaki
Tatsuya
T
Nitabaru
Naoya
N
Kumagai
Masakatsu
M
Shibasaki
D002384:Catalysis; D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry*; D007659:Ketones / Q000138:chemical synthesis / Q000737:chemistry*; D009570:Nitriles / Q000138:chemical synthesis* / Q000737:chemistry; D009943:Organophosphorus Compounds / Q000737:chemistry
D007097:Imines; D007659:Ketones; D009570:Nitriles; D009943:Organophosphorus Compounds; C015660:allyl cyanide