Zhou Pan, Ding Ling, Liu Yuxiu, Song Hongjian, Wang Qingmin
State Key Laboratory of Elemento-Organic Chemistry, Research Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Nankai University, Tianjin 300071, China.
Org Lett. 2024 Aug 30;26(34):7094-7099. doi: 10.1021/acs.orglett.4c02279. Epub 2024 Aug 16.
Four-membered ring structure is important in organic chemistry, and selective cleavage and functionalization of these strained rings are of great interest. However, direct α-functionalization of cyclobutanols is rarely reported because of the high O-H bond dissociation energy and the occurrence of β-scission of C-C bonds in these alcohols. Recently, transition-metal catalysis has facilitated alkoxy radical generation. Herein, we report a method for electrophotochemical α-functionalization of a silylcyclobutanol via visible-light-induced LMCT reactions of M-alkoxy complexes. Introduction of the silyl group into the cyclobutanol structure favored fast [1,2]-silyl transfer over ring opening, thus allowing the generation of α-functionalized products.
四元环结构在有机化学中很重要，这些张力环的选择性裂解和官能团化备受关注。然而，由于环丁醇中O-H键的高解离能以及这些醇中C-C键的β-断裂的发生，环丁醇的直接α-官能团化很少被报道。最近，过渡金属催化促进了烷氧基自由基的产生。在此，我们报道了一种通过M-烷氧基配合物的可见光诱导的光激发电子转移反应实现硅基环丁醇的光电化学α-官能团化的方法。将硅基引入环丁醇结构有利于快速的[1,2]-硅基转移而不是开环，从而能够生成α-官能团化产物。
