一价铜催化的酮或酮亚胺的不对称烯丙基化反应研究进展  

Research Progress on Copper(I)-Catalyzed Asymmetric Allylation of Ketones or Ketimines

作　　者：李晖[1] 殷亮 Li Hui;Yin Liang(Department of Applied Chemistry,Yuncheng University,Yuncheng 044000,China;Key Laboratory of Fluorine and Nitrogen Chemistry and Advanced Materials,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032,China)

机构地区：[1]运城学院应用化学系,运城044000 [2]中国科学院上海有机化学研究所先进氟氮材料重点实验室,上海200032

出　　处：《化学学报》2024年第12期1274-1288,共15页Acta Chimica Sinica

基　　金：国家自然科学基金(No.22271302);山西省自然科学基金(No.202303021211189)资助。

摘　　要：手性高烯丙基叔醇和相应的高烯丙基胺结构单元广泛存在于天然产物和药物分子中.因此,其不对称合成受到合成化学家们的重视.过渡金属催化的酮或酮亚胺的不对称烯丙基化反应具有优秀的原子经济性和步骤经济性,是合成手性高烯丙基叔醇和相应的高烯丙基胺最直接有效的方法之一.此综述着重介绍了一价铜催化的酮或酮亚胺不对称烯丙基化反应的研究进展.根据生成烯丙基一价铜物种的不同方式,将反应分为转金属化反应、三组分偶联反应和质子转移反应.另外,对一些具有代表性的反应机理和产物的合成应用做了简要介绍,并对该领域的发展进行了展望.Chiral tertiary homoallylic alcohol and chiralα,α-disubstituted homoallylic amine scaffolds are ubiquitous in numerous bioactive natural products and pharmaceutically relevant molecules.Thus,asymmetric synthesis of these com pounds has attracted an increasing attention from synthetic chemists.Compared to traditional methods,transi tion-metal-catalyzed asymmetric allylation of ketones or ketimines serves as a powerful methodology for constructing these compounds due to its excellent atom-and step-economy.Recent progress on copper(I)-catalyzed asymmetric allylation of ketones or ketimines is summarized.Based on the strategies for the generation of allyl-copper(I)species in situ,this review is divided into three sections:reactions through transmetalation,three-component coupling reactions,and proton-transfer reac tions.The mechanisms and potential applications of some representative strategies are also included.Finally,the future de velopments in this field are outlooked.

关 键 词：一价铜催化 酮 酮亚胺 不对称烯丙基化反应 转金属化反应 三组分偶联反应 质子转移反应 

分 类 号：O62[理学—有机化学]