New chiral N-heterocyclic olefin bifunctional organocatalysis inα-functionalization of β-ketoesters

被引：0

作者：

Sijing Wang ^{[1
]}

Cefei Zhang ^{[1
]}

Da Li ^{[1
]}

Yuqiao Zhou ^{[1
]}

Zhishan Su ^{[1
]}

Xiaoming Feng ^{[1
]}

Shunxi Dong ^{[1
]}

机构：

[1] Key Laboratory of Green Chemistry & Technology,Ministry of Education,College of Chemistry,Sichuan University

来源：

Science China(Chemistry) | 2023年 / 66卷 / 01期

基金：

中国国家自然科学基金;

关键词：

D O I：

暂无

中图分类号：

O621.251 [];

学科分类号：

070303 ; 081704 ;

摘要：

N-heterocyclic olefins(NHOs) possess an electron-rich and highly polarized C=C double bond due to the donating property of nitrogen atoms.This feature imparts exocyclic carbon atom of NHOs with strong basicity and high nucleophilicity.Although NHOs have been emerging as a new type of organocatalyst and ligand for metal complexes in organic synthesis,chiral NHOmediated highly enantioselective organic transformations were still elusive.Herein,we developed a new type of chiral aminederived C2-symmetric NHOs and employed them as efficient chiral bifunctional organocatalysts for asymmetric α-functionalization of β-ketoesters.With as low as 0.1 mol% catalyst loading,the desired amination and trifluoromethylthiolation products were afforded in good yields with high enantioselectivities(up to 99% yield and 99% ee).Experimental studies and theoretical calculation disclosed that hydrogen-bonding interaction upon protonation and other weak interaction between substrate and catalyst were crucial for the enantiocontrol.

引用

页码：147 / 154

页数：8