Premium
Chiral Silver Amides as Effective Catalysts for Enantioselective [3+2] Cycloaddition Reactions
Author(s) -
Yamashita Yasuhiro,
Imaizumi Takaki,
Guo XunXiang,
Kobayashi Shū
Publication year - 2011
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201100246
Subject(s) - cycloaddition , chemistry , enantioselective synthesis , pyrrolidine , catalysis , amide , ligand (biochemistry) , trimethylsilyl , organic chemistry , combinatorial chemistry , biochemistry , receptor
Asymmetric [3+2] cycloaddition of α‐aminoester Schiff bases with substituted olefins is one of the most efficient methods for the preparation of chiral pyrrolidine derivatives in optically pure form. In spite of its potential utility, applicable substrates for this method have been limited to Schiff bases that bear relatively acidic α‐hydrogen atoms. Here we report a chiral silver amide complex for asymmetric [3+2] cycloaddition reactions . A silver complex prepared from silver bis(trimethylsilyl)amide (AgHMDS) and ( R )‐DTBM‐SEGPHOS worked well in asymmetric [3+2] cycloaddition reactions of α‐aminoester Schiff bases with several olefins to afford the corresponding pyrrolidine derivatives in high yields with remarkable exo ‐ and enantioselectivities. Furthermore, α‐aminophosphonate Schiff bases, which have less acidic α‐hydrogen atoms, also reacted with olefins with high exo ‐ and enantioselectivities. The stereoselectivities of the [3+2] cycloadditions with maleate and fumarate suggested that the reaction proceeded by means of a concerted mechanism. An NMR spectroscopic study indicated that complexation of AgHMDS with the bisphosphine ligand was not complete, and that free AgHMDS, which did not show any significant catalytic activity , existed in the catalyst solution. This means that significant ligand acceleration occurred in the current reaction system.