Graduate School of Pharmaceutical Sciences, Chiba University.
Chem Pharm Bull (Tokyo). 2021;69(12):1170-1178. doi: 10.1248/cpb.c21-00757.
The ability to control the reactions of highly active chemical species to enable straightforward synthesis of valuable compounds such as bioactive natural products and pharmaceuticals is a continuing challenge in synthetic organic chemistry. This review describes the development of a methodology using reactive metal-carbene species and its synthetic application in our laboratory. First, regioselective synthesis of γ-amino acid equivalents to take advantage of their metal-dependent reactivities and the mechanistic rationale are presented. Chemoselective and enantioselective dearomatization reactions of several arenes with silver-carbene are also discussed. In the second half of the review, we discuss a carbene-insertion reaction into an amide and urea C-N bond for the assembly of nitrogen-bridged cyclic molecules.
能够控制高活性化学物质的反应，从而能够直接合成有价值的化合物，如生物活性天然产物和药物，这是合成有机化学中的一个持续挑战。本综述描述了使用反应性金属卡宾物种的方法的发展及其在我们实验室中的合成应用。首先，介绍了利用其金属依赖性反应性和机理原理进行γ-氨基酸等价物的区域选择性合成的方法。还讨论了银卡宾对几种芳烃的选择性和对映选择性脱芳构化反应。在综述的后半部分，我们讨论了酰胺和脲 C-N 键中卡宾插入反应，用于组装氮桥环分子。
