Chu W.-D, Zhang L, Zhang Z, Zhou Q, Mo F, Zhang Y, Wang J * Peking University, Beijing
and State Key Laboratory of Organometallic Chemistry, Shanghai, P. R. of China
Enantioselective Synthesis of Trisubstituted Allenes via Cu(I)-Catalyzed Coupling
of Diazoalkanes with Terminal Alkynes.
J. Am. Chem. Soc. 2016;
138: 14558-14561
Key words
copper - allenes - diazoalkenes - alkynes - enantioselective coupling
Significance
An enantioselective coupling reaction of aryldiazoalkanes with terminal alkynes is
described. A copper complex promotes this transformation to afford trisubstituted
allenes with high enantioselectivities. A rational stereocontrol model is proposed.
Comment
This reaction involves copper(I) carbene formation, alkynyl migratory insertion,
and protonation. The authors suggest that migratory insertion of the copper(I) carbene
species is the enantiodetermining step.
