未活化脂肪族体系的Csp-H三氟甲基化反应
Csp-H Trifluoromethylation of Unactivated Aliphatic Systems.
作者信息
He Jiachen, Nguyen Truong N, Guo Shuo, Cook Silas P
机构信息
Department of Chemistry, Indiana University, 800 East Kirkwood Avenue, Bloomington, Indiana 47405-7102, United States.
出版信息
Org Lett. 2021 Feb 5;23(3):702-705. doi: 10.1021/acs.orglett.0c03891. Epub 2021 Jan 14.
Abstract
A straightforward method for the undirected trifluoromethylation of unactivated methylene units was developed. The reaction proceeds in aqueous acetonitrile with Grushin's reagent, bpyCu(CF), under broad-spectrum white-light irradiation. The trifluoromethylation tolerates a wide range of functional groups including ketones, esters, nitriles, amides, alcohols, and carboxylic acids. The C-H cleavage step is performed via intermolecular H atom abstraction, and the selectivities across a range of methylene units are reported. Mechanistic studies offer a general reaction coordinate for the overall transformation.
摘要
开发了一种用于未活化亚甲基单元的无定向三氟甲基化的直接方法。该反应在乙腈水溶液中，在广谱白光照射下，使用格鲁申试剂bpyCu(CF)进行。三氟甲基化反应能耐受包括酮、酯、腈、酰胺、醇和羧酸在内的多种官能团。C-H键断裂步骤通过分子间氢原子提取进行，并报道了一系列亚甲基单元的选择性。机理研究为整个转化过程提供了一个通用的反应坐标。
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