苯胺
化学
艾地明
配体(生物化学)
苯甲醇
催化作用
偶联反应
亚胺
组合化学
胺气处理
戒指(化学)
金属
酒
反应机理
有机化学
受体
生物化学
作者
Adwitiya Pal,Krishna Mohan Das,Arunabha Thakur
标识
DOI:10.1021/acs.joc.3c00682
摘要
The acceptorless dehydrogenative coupling (ADC) between alcohols and amines to produce imines has been achieved mostly by employing precious-metal-based complexes or complexes of earth-abundant metal ions with sensitive and complicated ligand systems as catalysts mostly under harsh reaction conditions. Methodologies using readily available earth-abundant metal salts as catalysts without the requirement of ligand, oxidant, or any external additives are not explored. We report an unprecedented microwave-assisted CoCl2-catalyzed acceptorless dehydrogenative coupling of benzyl alcohol and amine for the synthesis of E-aldimines, N-heterocycles, and H2 under mild condition, without any complicated exogenous ligand template, oxidant, or other additives. This environmentally benign methodology exhibits broad substrate scope (43 including 7 new products) with fair functional-group tolerance on the aniline ring. Detection of metal-associated intermediate by gas chromatography (GC) and HRMS, H2 detection by GC, and kinetic isotope effect reveal the mechanism of this CoCl2-catalyzed reaction to be via ADC. Furthermore, kinetic experiments and Hammett analysis with variation in the nature of substituents over the aniline ring reveal the insight into the reaction mechanism with different substituents.
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