Molecular Catalyst Research Center , Chubu University , 1200, Matsumoto-cho , Kasugai , Aichi 487-8501 , Japan.
J Org Chem. 2018 May 4;83(9):4889-4904. doi: 10.1021/acs.joc.7b03180. Epub 2018 Mar 6.
The development of highly efficient reactions at only the desired position is one of the most important subjects in organic chemistry. Most of the reactions in current organic chemistry are reagent- or catalyst-controlled reactions, and the regio- and stereoselectivity of the reactions are determined by the inherent nature of the reagent or catalyst. In sharp contrast, substrate-directed reaction determines the selectivity of the reactions by the functional group on the substrate and can strictly distinguish sterically and electronically similar multiple reaction sites in the substrate. In this Perspective, three topics of substrate-directed reaction are mainly reviewed: (1) directing group-assisted epoxidation of alkenes, (2) ring-opening reactions of epoxides by various nucleophiles, and (3) catalytic peptide synthesis. Our newly developed synthetic methods with new ligands including hydroxamic acid derived ligands realized not only highly efficient reactions but also pinpointed reactions at the expected position, demonstrating the substrate-directed reaction as a powerful method to achieve the desired regio- and stereoselective functionalization of molecules from different viewpoints of reagent- or catalyst-controlled reactions.
仅在所需位置上开发高效反应是有机化学中最重要的课题之一。当前有机化学中的大多数反应都是试剂或催化剂控制的反应，反应的区域和立体选择性取决于试剂或催化剂的固有性质。相比之下，底物导向反应通过底物上的官能团来决定反应的选择性，并可以严格区分底物中空间和电子相似的多个反应位点。在这篇观点文章中，主要综述了底物导向反应的三个主题：（1）烯烃的导向基团辅助环氧化反应，（2）各种亲核试剂对环氧化物的开环反应，以及（3）催化肽合成。我们使用包括衍生自羟肟酸的配体在内的新型配体开发的新合成方法不仅实现了高效反应，而且还精确地在预期位置上进行了反应，这表明底物导向反应是一种强大的方法，可以从试剂或催化剂控制反应的不同角度实现所需的区域和立体选择性官能化。
