镍催化氮杂环丙烷的开环偶联反应研究  

Recent Advances in Nickel-Catalyzed Ring Opening Cross-Coupling of Aziridines

作　　者：陈健强 朱钢国[1] 吴劼 Chen Jianqiang;Zhu Gangguo;Wu Jie(Key Laboratory of the Ministry of Education for Advanced Catalysis Materials,Zhejiang Normal University,Jinhua,Zhejiang 321004;School of Pharmaceutical and Chemical Engineering&Institute for Advanced Studies,Taizhou University,Taizhou,Zhejiang 318000;State Key Laboratory of Organometallic Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences,Shanghai 200032)

机构地区：[1]浙江师范大学先进催化材料教育部重点实验室,浙江金华321004 [2]台州学院医药化工学院&高等研究院,浙江台州318000 [3]中国科学院上海有机化学研究所金属有机化学国家重点实验室,上海200032

出　　处：《化学学报》2024年第2期190-212,共23页Acta Chimica Sinica

基　　金：国家自然科学基金(No.22201201);浙江省自然科学基金(No.LY23B020001);浙江省万人计划项目(No.2020R52021)资助。

摘　　要：氮杂环丙烷类化合物是重要的有机合成子,其广泛存在于各种有机合成反应当中.因其独特的三元环结构,致使其具有较大的环张力.通常氮杂环丙烷类化合物可以与各种亲核试剂反应,合成各种传统方法难以合成的β-位取代的胺类化合物,其中包括氨基醇、氨基醚以及二胺类化合物.通过亲核试剂开氮杂环丙烷的反应研究已经相当成熟,此处不再赘述.此外,过渡金属催化的C—N活化是一类重要的合成方法.作为C—N活化重要底物,过渡金属催化氮杂环丙烷的开环偶联反应取得长足的发展.尤其是近十年来,镍催化氮杂环丙烷的开环偶联反应不断涌现.基于此,综述了镍催化在氮杂环丙烷开环偶联反应中的研究进展和设计原则,重点介绍氮杂环丙烷的开环原理,对比不同取代的氮杂环丙烷区域选择性,总结不同催化模式下的共性.本综述将从以下三个方面介绍氮杂环丙烷的开环偶联反应:其一是单独的镍催化模式;其二是光/镍协同共催化模式;其三则是电化学促进的镍催化模式.对于氮杂环丙烷的开环模式则可以分为:镍催化的SN2型亲核开环模式、卤素离子亲核开环模式以及电化学还原模式.Aziridines are among the most important building blocks in modern organic synthesis due to their proclivity to ring-opening with a wide range of nucleophiles.This small nitrogen-containing ring system is a highly strained molecule,and C—N fragmentation allows it to be used as the precursor for various scaffolds(including amino alcohols,amino ethers,and diamines)that are not readily accessible through conventional methods.The driving force for this C—N activation is the release of ring strain.In conclusion,significant advances in this filed have been realized with various of nucleophiles.On the other hand,the use of transition metal for C—N activation is one of the most significant methods for the construction of complex molecules.Transition metal-catalyzed ring opening cross-coupling of aziridines have received much attention in recent years.Over the past decades,many groups have described approaches to engage aziridines as electrophiles in nick-el-catalyzed cross-coupling.This paper reviews the recent advances in nickel-catalyzed ring opening cross-coupling of aziri-dines,focuses on the ring-opening methodology,compares the regioselective of the different aziridines,and summarizes gen-eralities of these strategies.We split this paper into three sections consisting of construction ofβ-functionalized amines via Ni-catalyzed,dual photoredox/Ni-catalyzed,and Ni-catalyzed electrochemical cross-coupling of aziridines.Traditional methods for the ring-opening of aziridines include(1)nickel-catalyzed SN2 nucleophilic ring-opening,(2)nucleophilic halide ring-opening,and(3)electro-induced ring-opening.

关 键 词：氮杂环丙烷 镍催化 光催化 C—N活化 自由基 

分 类 号：O621.251[理学—有机化学]