Copper-catalyzed asymmetric conjugate addition of Grignard reagents to cyclic enones
Copper-catalyzed asymmetric conjugate addition of Grignard reagents to cyclic enones
复制标题
DOI：
10.1073/pnas.0308008101
复制
发表时间：
2004-04-20
影响因子：
11.1
通讯作者：
Minnaard, AJ
中科院分区：
文献类型：
--
作者：
Feringa, BL;Badorrey, R;Minnaard, AJ
在铜催化的有机金属化合物与环烯酮的不对称共轭加成反应中，不再需要使用二烷基锌试剂来获得>95%的对映选择性。我们现在报告如何可以通过使用廉价和容易获得的格氏试剂来实现。双齿配体的筛选提供了市售手性二茂铁基二膦，特别是TaniaPhos和JosiPhos衍生物的铜配合物的出色结果。这些催化剂容忍一系列的格氏试剂和不同的环状烯酮作为底物，导致高的区域选择性和前所未有的对映选择性。此外，反应是成功的，在温和的条件下，在温和的催化剂负载量（5摩尔%）和添加剂的情况下。
It is no longer necessary to use dialkylzinc reagents to obtain enantioselectivities >95% in the copper-catalyzed asymmetric conjugate addition of organometallic compounds to cyclic enones. We now report how this can be accomplished by using inexpensive and readily available Grignard reagents. Screening of bidentate ligands provided outstanding results with copper complexes of commercially available chiral ferrocenyl-based diphosphines, in particular TaniaPhos and JosiPhos derivatives. These catalysts tolerate a range of Grignard reagents and different cyclic enones as substrates, leading to high regioselectivities and unprecedented enantioselectivities. Moreover, the reactions are successful with moderate catalyst loading (5 mol %) under mild conditions and in the absence of additives.