Department of Chemistry, Center for Excellence in Molecular Synthesis, University of Science and Technology of China, Hefei, Anhui 230026, P. R. China.
Org Lett. 2023 Mar 24;25(11):1883-1888. doi: 10.1021/acs.orglett.3c00398. Epub 2023 Mar 13.
By merging C-C and C-F bond cleavage, we developed a regioselective ring opening/-difluoroallylation of cyclopropyl ketones with α-trifluoromethylstyrenes, which proceeds under the catalysis of iron with the combination of manganese and TMSCl as the reducing agents, providing a new entry to the synthesis of carbonyl-containing -difluoroalkenes. Remarkably, the ketyl radical-induced selective C-C bond cleavage and the following generation of more-stable carbon-centered radicals enable complete regiocontrol of this ring opening reaction for various substitution patterns of the cyclopropane ring.
通过结合 C-C 和 C-F 键的断裂，我们开发了一种在铁催化下，使用锰和 TMSCl 作为还原剂，对环丙基酮与α-三氟甲基苯乙烯进行区域选择性开环/-二氟烯丙基化反应，为合成含羰基的 -二氟烯烃提供了新途径。值得注意的是，酮自由基诱导的选择性 C-C 键断裂和随后生成更稳定的碳中心自由基，使得这种开环反应对于环丙烷环的各种取代模式具有完全的区域选择性控制。
