Liu Xiaochen, Hee Samual, Sapir Netanel G, Li Alvin, Liu Jianbo, Chen Yu
Department of Chemistry and Biochemistry, Queens College of the City University of New York, 65-30 Kissena Blvd., Queens, New York 11367, United States.
Ph.D. Program in Chemistry, The Graduate Center of the City University of New York, 365 Fifth Ave., New York, New York 10016, United States.
Adv Synth Catal. 2024 Jun 10;366(11):2489-2494. doi: 10.1002/adsc.202301505. Epub 2024 Apr 9.
-BuNI/KSO mediated transformylation from -anisaldehyde to primary amides is reported. The mechanistic studies suggest the reaction occurs via a single electron transfer pathway. Based on the DFT electronic structure calculations of various reaction pathways, the most plausible mechanism involves the formation of a phenyl radical cation and an arenium ion as the key intermediates. It represents the first example where -anisaldehyde is employed as a formyl source via a non-metal mediated Csp-Csp bond cleavage.
报道了BuNI/KSO介导的从对茴香醛到伯酰胺的甲酰化反应。机理研究表明该反应通过单电子转移途径发生。基于对各种反应途径的DFT电子结构计算，最合理的机理涉及形成苯基自由基阳离子和芳鎓离子作为关键中间体。这是首次通过非金属介导的Csp-Csp键裂解将对茴香醛用作甲酰基源的例子。
