Enantioselective synthesis of chiral allenoates by guanidine-catalyzed isomerization of 3-alkynoates.
We report that chiral bicyclic guanidine 1 is found to catalyze the isomerization of alkynes to chiral allenes with high enantioselectivities. This Brønsted base catalyzed 1,3-proton shift reaction, an efficient and atom economical reaction, proceeds through deprotonation and protonation sequences. The axial chirality of the allenes is efficiently transferred to functionalized butenolides and cycloaddition products. We also successfully demonstrate the stereospecific synthesis of butenolide through allenoate cyclization with a catalytic cationic Au(I) complex.
Department of Chemistry, 3 Science Drive 3, National University of Singapore, Singapore 117543.
Hongjun
H
Liu
Dasheng
D
Leow
Kuo-Wei
KW
Huang
Choon-Hong
CH
Tan