铜催化剂促进的有机硼试剂与常见烯酮的不对称共轭加成反应。

Asymmetric Conjugate Addition of Organoboron Reagents to Common Enones Using Copper Catalysts.

机构信息

Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University , 21 Nanyang Link, Singapore 637371.

College of Science, Sichuan Agricultural University , Ya'an, Sichuan, China 625014.

出版信息

J Am Chem Soc. 2016 Jan 27;138(3):742-5. doi: 10.1021/jacs.5b11441. Epub 2016 Jan 15.

DOI:10.1021/jacs.5b11441

PMID:26756835

Abstract

Copper complexes of phosphoramidites efficiently catalyzed asymmetric addition of arylboron reagents to acyclic enones. Importantly, rare 1,4-insertion of arylcopper(I) was identified which led directly to O-bound copper enolates. The new mechanism is fundamentally different from classical oxidative addition/reductive elimination of organocopper(I) on enones.

摘要

膦酰胺配体的铜配合物能高效催化芳基硼酸试剂对环外烯酮的不对称加成。重要的是，鉴定到了罕见的芳基铜（I）的 1,4-插入，其直接生成了 O 配位的铜烯醇化物。新的反应机理与经典的烯酮上的有机铜（I）的氧化加成/还原消除有根本的不同。