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.
Yazaki
Ryo
R
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.
Nitabaru
Tatsuya
T
Kumagai
Naoya
N
Shibasaki
Masakatsu
M
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