P-手性化合物的不对称催化合成研究进展  

Research Progress on Catalytic Asymmetric Synthesis of P-Chiral Compounds

作　　者：李晖[1] 殷亮 Li Hui;Yin Liang(Department of Applied Chemistry,Yuncheng University,Yuncheng,Shanxi 044000;CAS Key Laboratory of Synthetic Chemistry of Natural Substances,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032)

机构地区：[1]运城学院应用化学系,山西运城044000 [2]中国科学院上海有机化学研究所,中国科学院天然产物有机合成化学重点实验室,上海200032

出　　处：《有机化学》2022年第10期3183-3200,共18页Chinese Journal of Organic Chemistry

基　　金：山西省高等学校科技创新(No.2022L478);山西省回国留学人员科研基金(No.2020-141);运城学院院级项目(No.CY-2020022);国家自然科学基金(Nos.21871287,21922114);上海市科学技术委员会基金(Nos.20JC1417100,21XD1424800)资助项目.

摘　　要：P-手性结构单元广泛存在于具有生物活性和药物活性的化合物中,并且P-手性化合物可用作不对称催化的手性配体或有机小分子催化剂.因而,近二十年来P-手性化合物的不对称合成引起了化学家的广泛关注.利用动力学拆分和动态动力学拆分的策略,以不对称的方式构建新的P—C、P—O或P—N键,将外销旋的仲膦、其硼烷加合物或其氧化物转变为相应的P-手性化合物是合成该类化合物最有效、最直接的方法之一.此综述从动力学拆分和动态动力学拆分两个策略出发,介绍P-手性化合物的不对称过渡金属催化合成方法及最新研究进展.根据亲电试剂的不同,将反应分为芳基化反应、对活泼烯烃或炔烃的加成反应、烷基化反应以及其它反应.此外,还介绍了通过构建不对称P—C键将前手性的伯膦转变为P-手性仲膦的反应.P-Chiral compounds are a valuable class of privileged structures in pharmaceutically and biologically active compounds and also serve as powerful and versatile ligands or organocatalysts in asymmetric synthesis. Therefore, their asymmetric synthese has gained increasing attention in the past two decades. By means of kinetic resolution(KR) or dynamic kinetic resolution(DKR) strategy, racemic secondary phosphines, their borane-adducts or their oxides can be transformed to the associated compounds with P-chirality, which serves as a straightforward and efficient protocol to construct a P-chiral center. The recent achievements of the transition-metal-catalyzed asymmetric syntheses of P-chiral compounds based on KR and DKR of racemic secondary phosphines, their borane-adducts and their oxides in the past two decades are summarized. Meanwhile, arylation, addition to activated alkenes or alkynes, alkylation and other reactions are covered respectively based on the varied reaction partners. These reaction entails the formation of new P—C, P—O and P—N bonds in an asymmetric manner.What’s more, the transformation of prochiral primary phosphines to P-chiral secondary phosphines is mentioned in the miscellaneous reaction section.

关 键 词：P-手性化合物 过渡金属催化 不对称催化 动力学拆分 动态动力学拆分 

分 类 号：O621.251[理学—有机化学]