Synthesis and Solid State Pharmaceutical Centre, Centre for Synthesis and Chemical Biology, School of Chemistry, University College Dublin, Dublin 4, Ireland.
Chem Soc Rev. 2021 Mar 7;50(5):3013-3093. doi: 10.1039/d0cs00702a. Epub 2021 Feb 5.
Oxa- and azabicyclic alkenes can be readily activated by transition-metal complexes with facial selectivity, because of the intrinsic reactivity of strained bicyclic structures. Synthetically, these compounds are important synthons that offer an important platform for the construction of biologically/medicinally significant compounds with two or more stereocenters. This Review comprehensively compiles the diverse catalytic processes involving the enantioselective transformations of oxa- and azabicyclic alkenes. It has been organized according to reaction type, including asymmetric ring opening (ARO) reactions, hydrofunctionalizations, cycloadditions and C-H activation reactions. The ARO section has been subdivided based on the type of nucleophiles employed, and further subdivided based on the metal used, with a separate topic dedicated to asymmetric ring-opening metathesis. Lastly, the presentation of each method/group of reactions is accompanied by concise discussions on their advantages and limitations.
氮杂和氧杂双环烯烃可以被过渡金属配合物容易地活化，这是由于双环结构的固有反应性。在合成方面，这些化合物是重要的合成子，为构建具有两个或更多手性中心的生物/医学相关化合物提供了重要平台。这篇综述全面总结了涉及氮杂和氧杂双环烯烃对映选择性转化的多种催化过程。它是根据反应类型组织的，包括不对称开环（ARO）反应、氢官能化、环加成和 C-H 活化反应。ARO 部分根据所使用的亲核试剂的类型进行细分，并根据所使用的金属进一步细分，其中专门有一个主题用于不对称开环复分解。最后，在介绍每种方法/反应组时，还附有对其优缺点的简明讨论。
