Copper‐Catalyzed Enantioselective Reductive Aldol Reaction of α,β‐Unsaturated Carboxylic Acids to Alkyl Aryl Ketones: Silanes as Activator and Transient Protecting Group
Copper‐Catalyzed Enantioselective Reductive Aldol Reaction of α,β‐Unsaturated Carboxylic Acids to Alkyl Aryl Ketones: Silanes as Activator and Transient Protecting Group
复制标题
铜催化α,β-不饱和羧酸对映选择性还原羟醛反应生成烷基芳基酮：硅烷作为活化剂和瞬时保护基团
DOI：
10.1002/chem.202104273
复制
发表时间：
2022
期刊：
影响因子：
--
通讯作者：
Matsuda Takanori
中科院分区：
文献类型：
--
作者：
Suzuki Hirotsugu;Yoneoka Kenji;Kondo Sora;Matsuda Takanori
在铜/双膦催化剂存在下，首次发展了α，β-不饱和羧酸的不受保护的对映选择性还原Aldol反应.该反应的特征在于通过氢硅烷原位保护和活化α，β-不饱和羧酸。原位形成的烯醇化铜与烷基芳基酮反应，得到具有优异的对映选择性（高达99%ee）的β-羟基羧酸。具有低催化剂负载的相应克级反应和β-羟基羧酸的衍生化突出了这种转化的实用性。
The first enantioselective reductive aldol reaction of unprotected α,β‐unsaturated carboxylic acids was developed by employing a copper/bisphosphine catalyst. The reaction features in situ protection and activation of an α,β‐unsaturated carboxylic acid by a hydrosilane. The copper enolate formed in situ reacts with an alkyl aryl ketone to afford the β‐hydroxy carboxylic acid with excellent enantioselectivity (up to 99 %ee). The corresponding gram‐scale reaction with a low catalyst loading and the derivatization of the β‐hydroxy carboxylic acids highlight the practicality of this transformation.