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. 2025 Aug 25;64(35):e202506157.
doi: 10.1002/anie.202506157. Epub 2025 Jul 31.

Regio-, Diastereo-, and Enantioselective Hydrosilylation of Alkyl gem-Difluoroalkenes to Construct Carbon and Silicon Stereogenic Centers

Huanhuan Li #  1 , Yan Qiao #  2 , Ming Li  1 , Fen Wu  1 , Hao Wu  1 , Junbiao Chang  1 , Dachang Bai  1
Affiliations

Regio-, Diastereo-, and Enantioselective Hydrosilylation of Alkyl gem-Difluoroalkenes to Construct Carbon and Silicon Stereogenic Centers

Huanhuan Li et al. Angew Chem Int Ed Engl. .

Abstract

The asymmetric hydrofunctionalization of aliphatic alkenes without auxiliary or stabilizing groups presents a significant challenge in modern organic synthesis. We report herein the nickel-catalyzed enantioselective hydrosilylation of alkyl-substituted gem-difluoroalkenes, which enables the generation of chiral α-difluoromethylsilanes with excellent regio- and enantioselectivity. Moreover, the simultaneous construction of carbon- and silicon-stereogenic centers was achieved with excellent diastereo- and enantioselectivity using prochiral silanes. This method provides an efficient approach to access sp3-enriched C-stereogenic centers equipped with high-value difluoromethyl groups. The resulting enantioenriched silanes could undergo a range of stereospecific transformations. Density functional theory (DFT) calculations were performed to elucidate the detailed mechanism.

Keywords: Alkyl gem‐difluoroalkenes; Hydrosilylation; Nickel catalysis; Silicon stereogenic center; α‐Difluoromethyl silanes.

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