The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-,diastereo-,and enantio-selectivity remains a paramount challenge.Herein we reported a novel protocol for the use...The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-,diastereo-,and enantio-selectivity remains a paramount challenge.Herein we reported a novel protocol for the use of highly enantioselective copper-catalyzed cycloaddition ofα,β-unsaturated acylsilanes as a springboard reaction for the facile synthesis of structurally diversified pyrrolidines and complicatedα-amino esters by desilylation.The newly developed process could provide a wide range of synthetically useful acylsilane-substituted pyrrolidines(ASiP)in high yields and excellent diastereo-and enantioselectivities with Cu/(R)-XylBINAP complex as the catalyst.And the downstream desilylation transformation enables to expand the potntial applications of 1,3-dipolar cycloaddition in the construction of structurally unique amino acid derivatives,in which an unprecedented and concerted fluoride anion-promoted C–X(X=H,Si,N,C)bond cleavage occurred to the enantioselective construction of aldehyde-substituted pyrrolidines,linear cinnamaldehyde or alkene-substituted amino esters in high ee values.展开更多
基金supported by the National Natural Science Foundation of China(21773051,21702211,21703051)Zhejiang Provincial Natural Science Foundation of China(LZ18B020001,LQ19B040001,LY18B020013)the Hangzhou Science and Technology Bureau of China(20180432B05)。
文摘The catalytic asymmetric synthesis of novel and chiral amino acid derivatives with unconventional chemo-,diastereo-,and enantio-selectivity remains a paramount challenge.Herein we reported a novel protocol for the use of highly enantioselective copper-catalyzed cycloaddition ofα,β-unsaturated acylsilanes as a springboard reaction for the facile synthesis of structurally diversified pyrrolidines and complicatedα-amino esters by desilylation.The newly developed process could provide a wide range of synthetically useful acylsilane-substituted pyrrolidines(ASiP)in high yields and excellent diastereo-and enantioselectivities with Cu/(R)-XylBINAP complex as the catalyst.And the downstream desilylation transformation enables to expand the potntial applications of 1,3-dipolar cycloaddition in the construction of structurally unique amino acid derivatives,in which an unprecedented and concerted fluoride anion-promoted C–X(X=H,Si,N,C)bond cleavage occurred to the enantioselective construction of aldehyde-substituted pyrrolidines,linear cinnamaldehyde or alkene-substituted amino esters in high ee values.
