摘要
电化学通过发展新的反应途径解决了合成化学中棘手的挑战,为分子的构建提供了一个强大的工具.本文发展了一种电化学选择性双氧化策略,以盐酸为双功能化试剂实现了从硫醚合成α-氯代亚砜.该策略底物范围广、具有高非对映选择性和区域选择性.重要的是,对氨基酸和药物衍生物的后期修饰进一步突出了该策略的实用性.此外,机理研究表明,阳极的双氧化过程是该选择性转化成功的关键.这种电化学双氧化策略可能具有广谱性,预计该策略在许多化学领域具有广泛应用.
Electrochemistry contributes a strong tool for the manufacture of molecules,addressing intractable challenges in synthetic chemistry by enabling innovative reaction pathways.Herein,a bifunctional reagent,aqueous hydrochloric acid,is used to establish an electrochemical selective dual-oxidation approach that gives access toα-chlorosulfoxides from sulfides.This strategy presents broad substrate scope,high diastereoselectivity,and regioselectivity.The late-stage modification of amino acids and pharmaceutical derivatives further highlights the utility.Furthermore,detailed mechanistic studies reveal that the key success for this selective chemical transformation is the dual-oxidation process at the anode.This electrochemical dual-oxidation strategy may have wide universality;we anticipate diverse applications of this protocol across the many fields of chemistry.
作者
王华敏
余明明
张盘月
万好
丛恒将
雷爱文
Huamin Wang;Mingming Yu;Panyue Zhang;Hao Wan;Hengjiang Cong;Aiwen Lei(The Institute for Advanced Studies(IAS),College of Chemistry and Molecular Sciences,Wuhan University,Wuhan 430072,China;Department of Chemical and Materials Engineering,King Abdulaziz University,Jeddah 21589,Saudi Arabia;National Research Center for Carbohydrate Synthesis,Jiangxi Normal University,Nanchang 330022,China)
基金
supported by the National Natural Science Foundation of China(22031008)
Science Foundation of Wuhan(2020010601012192)
The Program of Introducing Talents of Discipline to Universities of China(111 Program)is also appreciated。
关键词
合成化学
区域选择性
电化学
反应途径
亚砜
广谱性
硫醚
化学领域
Dual-oxidation
Diastereoselectivity
Sulfur-containing compounds
Electrochemistry
Regioselectivity