Cyanomethylzinc bromide

Enantioselective Addition of Cyanomethylzinc Bromide, Reformatsky Reagent, and Alkynylzinc Reagents to Aldehydes. The enantioselective additions of cyanomethylzinc... 

An optically active p-hydroxy nitrile with 40% ee is obtained from the reaction of LiCH2CN with PhCHO in the presence of (1). The same compound with higher ee (93% ee) is obtained using cyanomethylzinc bromide and the chiral ligand DPMPM. Amino alcohol (1) accelerates the basicity of BuLi. Thus methyl phenyl sulfide is deprotonated by BuLi in the presence of (1)... 

Enantioselective cyanomethylation. Cyanomethylzinc bromide, prepared by reaction of BrCH2CN with Zn/Cu, adds to aryl aldehydes in the presence of (S)-l (1 equiv.) to give / -hydroxy nitriles in 87-93% ee. If only 0.3 mol% of (S)-l is present the optical yield is markedly decreased (in the case of QIlsCHO cc falls from 93 to 78%). Therefore, 1 serves both as a ligand and a catalyst. 

---