1. Copper-catalyzed highly switchable defluoroborylation and hydrodefluorination of 1-(trifluoromethyl)alkynes.
- Author
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Xu, Jun, Yan, Zhao-Cheng, Liu, Li, Qin, Long, Fan, Xuan, Zou, Yu, Zhang, Qi, and Xu, Hua-Jian
- Subjects
DRUG discovery ,DENSITY functional theory ,LIGANDS (Chemistry) ,ORGANIC synthesis ,MATERIALS science - Abstract
CF
2 -containing compounds hold significant potential in drug discovery, organic synthesis, and materials science. However, synthesizing various CF2 -containing building blocks from a single compound remains challenging. Here, we present a Cu-catalyzed, switchable defluoroborylation and hydrodefluorination of trifluoromethylated alkynes, yielding four types of CF2 -containing compounds. The chemo- and regio-selective sp2 /sp3 1,2-diborylation and sp2 monoborylation of 1-(trifluoromethyl)alkynes are controlled by adjusting the solvent and ligand quantity. Additionally, altering the base allows selective generation of gem-difluoroalkenes or difluoromethylalkenes. Notably, our method prevents over-defluorination of the CF3 group on unsaturated C-C bonds during nucleophilic additions, preserving the pharmaceutically valuable CF2 group. Experimental data and density functional theory (DFT) calculations elucidate the regioselectivities of Cu-Bpin addition and the regulatory role of the ligand in selective deborylation processes. Achieving the modular synthesis of various CF2 -containing building blocks from a single compound remains a formidable challenge. Herein, the authors present a Cu-catalyzed switchable defluoroborylation and hydrodefluorination of trifluoromethylated alkynes, affording four types of synthetically challenging CF2 -containing compounds. [ABSTRACT FROM AUTHOR]- Published
- 2024
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