新型手性二茂铁基 P,S-配体用于高非对映选择性/对映选择性催化[3 + 2]环加成反应，其中包括亚胺叶立德与环状和非环状烯酮的反应。

New chiral ferrocenyl P,S-ligands for highly diastereo-/enantioselective catalytic [3 + 2] cycloaddition of azomethine ylides with cyclic and acyclic enones.

机构信息

Dalian Institute of Chemical Physics, Chinese Academy of Sciences, 457 Zhongshan Road, Dalian 116023, China.

出版信息

Org Lett. 2010 Dec 3;12(23):5542-5. doi: 10.1021/ol1024647. Epub 2010 Nov 11.

Abstract

A new family of chiral ferrocenyl P,S-ligands has been developed and successfully applied in a highly endo-selective catalytic asymmetric cycloaddition of azomethine ylides with various enones, including cyclic and acyclic α-enones. For cyclic α-enones, a [Cu(CH(3)CN)(4)]ClO(4)/(R(c),S(Fc))-2f complex catalyzed the cycloaddition to give the sole endo-cycloadducts in perfect enantioselectivities (normally 99% ee), while an AgOAc/(R(c),S(Fc))-2f catalytic system exhibited good endo/exo selectivities (endo/exo = 91/9 to 96/4) and high enantiocontrol (up to 98% ee) for acyclic α-enones.

摘要

一种新的手性二茂铁膦，硫配体家族已经被开发出来，并成功应用于高endo-选择性的催化不对称环加成亚胺叶立德与各种烯酮，包括环状和非环状的α-烯酮。对于环状的α-烯酮，[Cu(CH(3)CN)(4)]ClO(4)/(R(c),S(Fc))-2f 配合物催化环加成反应，以获得单一的endo-环加成产物，具有完美的对映选择性（通常为 99%ee），而 AgOAc/(R(c),S(Fc))-2f 催化体系对非环状的α-烯酮表现出良好的endo/exo 选择性（endo/exo = 91/9 至 96/4）和高对映体控制（最高达 98%ee）。