N-芳基酰胺类惰性C(aryl)-N键直接活化/官能化反应研究

N−芳基酰胺类化合物是非常重要的有机化合物。分子内的羰基C−N键的解离能 (95 kcal/mol)比芳基C−N键的解离能(104 kcal/mol)低，所以通常情况下，在反应过程中羰基C−N键优先发生反应，比如在水解反应中生成酸和芳胺类化合物。目前，有几例文献报道了N−芳基酰胺类化合物高选择性惰性芳基C-N键断裂反应，但是这些反应局限于一些三级的N−芳基酰胺类化合物。因此，区域专一的断裂二级和三级酰胺类化合物中的芳基C−N键而不影响分子内含有的羰基C−N键仍然是一项非常具有挑战性的工作。本项目拟系统地研究高碘试剂促进的高选择性裂解N−芳酰胺类化合物中惰性芳基C−N键的方法，开发利用该芳基C−N键活化/官能化反应制备多种功能化的芳基化合物和酰胺类化合物的通用新方法。同时通过对反应机理的研究，为其它惰性C−N键的直接活化/官能化反应提供实验支持和理论指导。

N-Arylamides are very important organic compounds. Commonly, the dissociation energy of the C(carbonyl)−N bond (95 kcal/mol) is lower than that of the C(aryl)−N bond (104 kcal/mol), thus the C(carbonyl)−N bond reacts preferentially in the reaction, for example in the hydrolysis reaction, to give the acids and arylamines. Currently, a few literatures have foucsed on the regioselective cleavage of inert C(aryl)−N bonds of N-aryl tertiary amides. Thus it can be seen that it remains a very challenging work to regioselective cleavage of the C(aryl)−N bond of the secondary and tertiary amides without touching the C(carbonyl)−N bond. This project intends to investigate the regioselective cleavage of the inert C(aryl)−N bond of N-arylamides in the presence of hypervalent organoiodine reagents systematically, and develop novel methods to get to various functionalized aromatic derivatives and amides based on the highly selective inert C(aryl)−N bond activation/functionalization reaction. This research might provide an experimental support and theoretical guidance for other C−N bond activation/functionalization reaction through the study of the reaction mechanism.