物理有机手段在铑催化的惰性键转换中的应用

Rhodium-catalyzed inert chemical bonds transformation and related mechanism investigation

本研究组过去几年中在过渡金属铑(Rh)催化的惰性化学键转换方面取得了一定的研究进展.从Rh( Ⅲ)催化的C–H键对亚胺、醛、酮及酯或酰胺类化合物的加成反应开始,对这类反应机理进行了系统深入的研究,在此基础上,开展了Rh(Ⅰ)催化的C–H键和羧酸的脱羰基偶联反应;Rh( Ⅲ)催化的通过C–C键断裂进而实现的烯基化、芳基化、还原断裂及有机分子片段转换反应;Rh(Ⅰ)催化的通过C–C键断裂进而实现的脱羰基化反应以及有机分子片段的快速重组反应.本文以这些研究为素材,展示了几种重要的物理研究手段,如同位素实验、竞争反应、活性中间体合成、动力学实验及计算化学在反应机理研究中的应用.

In the very recent years, we made some progress on Rh-catalyzed inert chemical bonds transformation. We start our research from Rh（Ⅲ）-catalyzed C–H additions to imines, aldehydes, ketones, esters and amides. After a systematic mechanism investigation, we found the key intermediate Rh（Ⅲ） complex is very important. Then the research was extended to Rh（Ⅰ）-catalyzed couplings between C–H bonds and carboxylic acids via CO release, Rh（Ⅲ）-catalyzed alkenylation, arylation, reductive cleavage and group transition by C–C cleavage via b-C elimination, Rh（I）-catalyzed decarbonylation and recombination between ketones and carboxylic acids by C–C cleavage via oxidative addition. Using these examples, we present the application of kinetic isotope effects, competitive experiments, key intermediate synthesis, kinetic characterization, computational studies on mechanism investigation.