NiH-Catalyzed Reductive Hydrocarbonation of Enol Esters and Ethers  

作　　者：Xiao-Xu Wang Lu Yu Xi Lu Zhi-Lin Zhang De-Guang Liu Changlin Tian Yao Fu 

机构地区：[1]Hefei National Laboratory for Physical Sciences at the Microscale,CAS Key Laboratory of Urban Pollutant Conversion,Anhui Province Key Laboratory of Biomass Clean Energy,Center for Excellence in Molecular Synthesis of CAS,University of Science and Technology of China,Hefei 230026 [2]Institute of Energy,Hefei Comprehensive National Science Center,Hefei 230031 [3]High Magnetic Field Laboratory,Chinese Academy of Sciences,Hefei 230031 [4]School of Life Sciences,University of Science and Technology of China,Hefei 230027

出　　处：《CCS Chemistry》2022年第2期605-615,共11页中国化学会会刊（英文）

基　　金：the National Natural Science Foundation of China(grant nos.21732006,51821006,21927814,and 51961135104);the Strategic Priority Research Program of CAS(grant nos.XDB20000000 and XDB37040000);the USTC Research Funds of the Double First-Class Initiative(grant no.YD3530002002);the Users with Excellence Program of Hefei Science Center CAS(grant nos.2019HSCUE017 and 2019HSC-UE005).

摘　　要：Chiral dialkyl carbinols and their derivatives are significant synthetic building blocks in organic chemistry and related fields.The development of convenient and efficient methods to access these compounds has long been an important endeavor.Herein,we report a NiH-catalyzed reductive hydroalkylation and hydroarylation of enol esters and ethers.α-Oxoalkyl organonickel species were generated in situ in a catalytic mode and then participated in cross-coupling with alkyl or aryl halides.This approach enabled C(sp^(3))–C(sp^(3))and C(sp^(3))–C(sp^(2))bond formation under mild reductive conditions with simple operations,thereby boosting a broad substrate scope and good functional compatibility.Esters of enantioenriched dialkyl carbinols were accessed in a catalytic asymmetric version.Mechanistic studies demonstrated that this reaction proceeded through a syn-addition of Ni–H intermediate to an enol ester with high regio-and enantioselectivity.

关 键 词：nickel hydride asymmetric synthesis radical coupling reductive hydroalkylation reductive hydroarylation enol ester enol ether 

分 类 号：O62[理学—有机化学]