铜催化的硼酸锂芳基正丁酯的二氟甲基化、一氟甲基化和一氟烷基化反应

IF 11.3 1区化学 Q1 CHEMISTRY, PHYSICAL ACS Catalysis Pub Date : 2025-03-04 DOI:10.1021/acscatal.4c07840

Feng Gao, Yisa Xiao, Zimeng Li, Qilong Shen

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Sulfonium Ylide Enabled, Copper-Catalyzed Difluoromethylation, Monofluoromethylation, and Monofluoroalkylation of Lithium Aryl nButyl Borates

A copper-catalyzed fluoroalkylation of lithium aryl ⁿbutyl borates with electrophilic fluoroalkylating reagent YlideFluor for the preparation of di-, trifluoromethyl-, and monofluoroalkyl-substituted (hetero)arenes under mild conditions was described. Control experiments indicated that a fluoroalkyl radical, rather than a difluorocarbene intermediate, is involved in the catalytic process. In addition, stoichiometric reactions demonstrated that transmetalation of copper catalyst with lithium aryl ⁿbutyl borate takes place before the single-electron-transfer (SET) oxidation of an ate-type Cu(I) intermediate [Cu^I(Ar)(SCN)]⁻ by YlideFluor. Based on these mechanistic results, a reasonable catalytic cycle for the copper-catalyzed fluoroalkylation of lithium aryl ⁿbutyl borates was proposed.

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来源期刊

ACS Catalysis CHEMISTRY, PHYSICAL-

CiteScore

20.80

自引率

6.20%

发文量

1253

审稿时长

1.5 months

期刊介绍： ACS Catalysis is an esteemed journal that publishes original research in the fields of heterogeneous catalysis, molecular catalysis, and biocatalysis. It offers broad coverage across diverse areas such as life sciences, organometallics and synthesis, photochemistry and electrochemistry, drug discovery and synthesis, materials science, environmental protection, polymer discovery and synthesis, and energy and fuels. The scope of the journal is to showcase innovative work in various aspects of catalysis. This includes new reactions and novel synthetic approaches utilizing known catalysts, the discovery or modification of new catalysts, elucidation of catalytic mechanisms through cutting-edge investigations, practical enhancements of existing processes, as well as conceptual advances in the field. Contributions to ACS Catalysis can encompass both experimental and theoretical research focused on catalytic molecules, macromolecules, and materials that exhibit catalytic turnover.