过渡金属催化的酰胺C－N键活化-北京大学.PDF

大学化学(Daxue Huaxue) June Univ. Chem. 2017, 32 (6), 1－12 1 ∙今日化学∙ doi: 10.3866/PKU.DXHX201702018 过渡金属催化的酰胺C－N键活化 陈天阳 张文雄* (北京大学化学与分子工程学院，北京100871) 摘要：过渡金属催化的酰胺C －N 键活化已成为有机化学和金属有机化学热门的研究领域之一。酰胺中 羰基C－N 键的切断可分为5 种不同模式：1) 氧化加成反应；2) 形成季铵盐后的酰基转移反应；3) 质子 解反应；4) 氢化反应；5) 脱羧反应。而酰胺非羰基C－N 键的切断可分为4 种不同模式：1) 氧化加成反 应；2) 亲核取代反应；3) 形成亚胺或亚胺盐；4) β-氨基消除反应。本文综述了近年来过渡金属催化的 酰胺中羰基C－N 键和非羰基C－N 键的不同切断模式。 关键词：酰胺；C－N 键切断；过渡金属催化 中图分类号：G64 ；O6 Transition-Metal-Catalyzed Cleavage of Amide C －－N Bonds CHEN Tian-Yang ZHANG Wen-Xiong* (College of Chemistry and Molecular Engineering, Peking University, Beijing 100871, P. R. China) Abstract: Transition-metal-catalyzed cleavage of amide C －N bonds has become one of the hot fields of organic chemistry and organometallic chemistry. The cleavage of amide carbonyl C －N bonds catalyzed by transition-metal catalysts can be mainly classified into five pathways: i) via oxidative addition, ii) via acyl migration in ammonium species, iii) via protonolysis, iv) via hydrogenation, and v) via decarboxylation. Transition-metal-catalyzed cleavage of amide non-carbonyl C －N bonds can be divided into four classes: i) via oxidative addition, ii) via nucleophilic attack, iii) via imine or iminium species, and iv) via β-amino elimination. This review briefly summarized the different modes of transition-metal-catalyzed cleavage of amide carbonyl and non-carbonyl C －N bonds in recent years. Key Words: Amides; Cleavage of C －N bonds; Transition-metal catalysis 酰胺是一类在自然界中普遍存在的含氮化合物，它是蛋白质的关键组成单元，在天然产物和人工