Shinji Harada

Utility of N-acylpyrroles as activated monodentate ester surrogates is demonstrated in several catalytic asymmetric reactions. In the direct Mannich-type reaction, the N-acylpyrrole was used as a donor, and an In(O-i-Pr)<sub>3</sub>/linked-BINOL complex efficiently promoted the Mannich-type reaction to produce β-amino-α-hydroxy carboxylic acid derivatives in high yield and ee (up to 96% ee). α,β-Unsaturated N-acylpyrroles were useful as activated ester equivalent acceptors. In the asymmetric epoxidation reaction using a Sm(O-i-Pr)<sub>3</sub>/H<sub>8</sub>-BINOL complex, high catalyst turnover number (up to 4720), high turnover frequency (up to >3000 h<sup>-1</sup>) and high ee (up to >99% ee)were realized. α,β-Unsaturated N-acylpyrroles were also effective substrates for asymmetric aza-Michael reaction. Heterobimetallic YLi<sub>3</sub>tris(binaphthoxide) complex promoted the aza-Michael reaction in high enantioselectivity (up to 94% ee).