摘要
氧化N-脱烷基化反应在药物代谢和有机合成中具有重要意义,但其选择性和底物普适性仍是挑战.本文系统综述了酶催化和仿生催化氧化N-脱烷基化反应,重点探讨了高价金属-氧中间体的作用机制及氢原子攫取(HAA)与电子转移(ET)路径的争议.研究表明,仿生催化体系通过调控配体结构和氧化剂类型,可实现温和条件下的高效、高选择性转化,并拓展了其在复杂分子(如生物碱和多肽)修饰或重构中的应用.
Oxidative N-dealkylation reaction plays a significant role in drug metabolism and organic synthesis,yet challenges remain in achieving high selectivity and substrate generality.This review systematically summarizes both the enzymatic and the biomimetic catalytic systems for oxidative N-dealkylation,with a focus on the mechanistic role of high-valent metal-oxo intermediates and the ongoing debate between hydrogen-atom abstraction(HAA)and electron-transfer(ET)pathways.Through tailored ligand design and oxidant selection,these studies demonstrate that biomimetic catalytic systems enable efficient and selective transformations under mild conditions,further expanding their applications in the modification or reconstruction of complex molecules(e.g.,alkaloids and peptides).
作者
刘悦华
吴春霞
陈洁
王斌
LIU Yuehua;WU Chunxia;CHEN Jie;WANG Bin(School of Chemistry and Chemical Engineering,University of Jinan,Jinan,Shandong 250022,China)
出处
《分子催化(中英文)》
北大核心
2025年第5期483-493,I0006,共12页
Journal of Molecular Catalysis(China)
基金
国家自然科学基金(No.22372071)
泰山学者计划(No.tsqn202408209).
关键词
仿生催化
选择氧化
N-脱烷基化
高价金属-氧中间体
biomimetic catalysis
selective oxidation
N-dealkylation
high-valent metal-oxo intermediates
