Tuning the Chiral Environment of C2-Symmetric Diene Ligands: Development of 3,7-Disubstituted Bicyclo[3.3.1]nona-2,6-dienes
Tuning the Chiral Environment of C2-Symmetric Diene Ligands: Development of 3,7-Disubstituted Bicyclo[3.3.1]nona-2,6-dienes
复制标题
DOI：
10.1021/jo802437h
复制
发表时间：
2009-01-16
影响因子：
3.6
通讯作者：
Hayashi, Tamio
中科院分区：
文献类型：
--
作者：
Shintani, Ryo;Ichikawa, Yoshitaka;Hayashi, Tamio
通过对双环[3.3.1]壬-2，6-二烯的结构分析，设计并合成了基于3，7-二取代双环[3.3.1]壬-2，6-二烯骨架的C2对称手性二烯配体1。这些手性配体容易与铑（I）结合，并提供与现有手性二烯不同的手性环境。由此获得的铑络合物作为有效的催化剂用于烯基-和芳基硼酸与各种α，β-不饱和酮的1，4-加成，包括以前难以提供高对映选择性的几种组合。
Through the structural analysis of bicyclo[3.3.1]nona-2,6-dienes, new C-2-symmetric chiral diene ligands 1 based on 3,7-disubstituted bicyclo[3.3.1]nona-2,6-diene framework have been designed and synthesized. These chiral ligands readily bind to rhodium(I) and provide a different chiral environment from the existing chiral dienes. The rhodium complexes thus obtained act as effective catalysts for 1,4-addition of alkenyl- and arylboronic acids to various alpha,beta-unsaturated ketones, including several combinations that were previously difficult to provide high enantioselectivity.