Chemical Engineering Science ( IF 4.1 ) Pub Date : 2022-08-01 , DOI: 10.1016/j.ces.2022.117960 Lanqing Deng , Lang Chen , Liangdi Zhu , Yang Li , Jie Ou-Yang , Shaofeng Wu , Peng Chen , Sheng Shen , Junkang Guo , Yongbo Zhou , Chak-Tong Au , Shuang-Feng Yin
Being extensively applied in various fields of chemistry and chemical industry, the development of a green and versatile method for the synthesis of amides is in line with the demand of sustainable chemistry. Herein, a direct, highly selective, and scale-up (5–20 mmol) method for photocatalytic synthesis of amides through aerobic oxidative amination of alcohols with amines was developed under visible light, room temperature, using air as the oxidant. Benefiting from the adsorption of sodium hemiaminal on catalyst lengthens the CH bond (1.148 Å), this novel process is feasible for a broad range of functionlized amides (69 examples), especially those for drug manufacture (e.g., moclobemide and pipobroman). Imines was almost prevented with excellent amide selectivity up to 99 % could be ascribed to the low energy barrier for hemiaminal dehydrogenation while that for dehydration is high (2.13 eV). This green and efficient protocol represents an ideal alternative to the currently known methods.
中文翻译:
在 Ag2O/P-C3N4 光催化剂上通过好氧氧化胺化合成酰胺的绿色、通用和放大合成
广泛应用于化学和化学工业的各个领域,开发绿色、通用的酰胺合成方法符合可持续化学的需求。在此,本文开发了一种直接、高选择性和放大(5-20 mmol)光催化合成酰胺的方法,该方法是在可见光、室温下,使用空气作为氧化剂,通过醇与胺的需氧氧化胺化来合成酰胺。受益于钠半胺在催化剂上的吸附延长了 CH 键 (1.148 Å),这种新工艺适用于广泛的官能化酰胺(69 个示例),尤其是用于药物制造的那些(例如,吗氯贝胺和哌泊溴)。亚胺几乎被阻止,酰胺选择性高达 99%,这可归因于半氨基脱氢的低能垒,而脱水的能垒高(2.13 eV)。这种绿色高效的协议代表了当前已知方法的理想替代方案。