平行成对电解促进的不对称催化:同时合成醛/芳基溴化物和手性醇  

Parallel paired electrolysis-enabled asymmetric catalysis:simultaneous synthesis of aldehydes/aryl bromides and chiral alcohols

作　　者：孙冰 王振华 王运召 顾玉诚 马聪 梅天胜 Bing Sun;Zhen-Hua Wang;Yun-Zhao Wang;Yu-Cheng Gu;Cong Ma;Tian-Sheng Mei(State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032,China;Syngenta,Jealott’s Hill International Research Centre,Berkshire RE426EY,UK)

机构地区：[1]State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,University of Chinese Academy of Sciences,Chinese Academy of Sciences,Shanghai 200032,China [2]Syngenta,Jealott’s Hill International Research Centre,Berkshire RE426EY,UK

出　　处：《Science Bulletin》2023年第18期2033-2041,M0003,M0004,共11页科学通报（英文版）

基　　金：supported by the National Key R&D Program of China(2021YFA1500100);the National Natural Science Foundation of China(21821002,21772222,91956112,and 22101294);the Science and Technology Commission of Shanghai Municipality of Shanghai(18JC1415600 and 20JC1417100);Syngenta(UK).And it is also dedicated to professor Li-Xin Dai on the occasion of his 100th birthday.

摘　　要：金属催化的不对称电还原偶联已成为有机合成的强有力工具,但是这类反应通常需要牺牲试剂或者牺牲阳极来获得电中性。同时利用阳极和阴极作为工作电极可以很好地解决该问题,然而也面临着诸多挑战:(1)完美匹配阳极氧化和阴极还原反应的电位和速率:(2)精确控制金属氧化态和对映选择性:(3)底物与底物/产物之间的副反应将降低该反应的效率:本文作者开发了一种平行成对电解(PPE)促进的不对称催化新模式,在未分隔的电解池中,利用阳极和阴极分别氧化和还原醇和酮,这两个底物最终同时以较高的产率和对映选择性转化为相应的醛和手性叔醇,除此之外,这种镍催化的不对称还原偶联可以很好地匹配(杂)芳烃的阳极氧化C-H键溴化。该方案为有机电化学的不对称合成提供了新思路。Metal-catalyzed asymmetric electro-reductive couplings have emerged as a powerful tool for organic synthesis,wherein a sacrificial anode is typically required.Herein,a parallel paired electrolysis(PPE)-enabled asymmetric catalysis has been developed,and the alcohols and ketones could be simultaneously converted to the corresponding aldehydes and chiral tertiary alcohols with high yields and enantioselectivity in an undivided cell.Additionally,this Ni-catalyzed asymmetric reductive coupling can well match the anodic oxidative C-H bond bromination of(hetero)arenes.This protocol opens an alternative avenue for organic synthesis.

关 键 词：Organic electrochemistry Nickel catalysis Parallel paired electrolysis Asymmetric catalysis 

分 类 号：TQ223.1[化学工程—有机化工] TQ213TQ426