Diboron-mediated palladium-catalyzed asymmetric transfer hydrogenation using the proton of alcohols as hydrogen source  

作　　者：Bo Wu Jimin Yang Shu-Bo Hu Chang-Bin Yu Zi-Biao Zhao Yi Luo Yong-Gui Zhou 

机构地区：[1]Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Dalian 116023,China [2]State Key Laboratory of Fine Chemicals,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China [3]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China

出　　处：《Science China Chemistry》2021年第10期1743-1749,共7页中国科学（化学英文版）

基　　金：the National Natural Science Foundation of China(21901239,21532006);the Strategic Priority Program of Chinese Academy of Sciences(XDB17020300,QYZDJ-SSW-SLH035)。

摘　　要：The developments of hydrogen sources stand at the forefront of asymmetric reduction. In contrast to the well-studied alcohols as hydrogen sources via β-hydride elimination, the direct utilization of the proton of alcohols as a hydrogen source for activatormediated asymmetric reduction is rarely explored. Herein we report the proton of alcohols as a hydrogen source in diboronmediated palladium-catalyzed asymmetric transfer hydrogenation of 1,3-diketones and indoles, providing a series of chiral β-hydroxy ketones and indolines with excellent yields and enantioselectivities. This strategy would be useful for the synthesis of chiral deuterium-labelled compounds due to the ready availability of deuterium-labelled alcohols. Mechanistic investigations and DFT calculations revealed that active chiral Pd-H species was generated from the proton of alcohols by activating of tetrahydroxydiboron, hydrogen transfer was the rate-determining step, and the reaction preferred Pd(0)-catalyzed mechanism.

关 键 词：proton of alcohols hydrogen source asymmetric reduction 

分 类 号：O621.251[理学—有机化学]