Nickel-catalyzed regiodivergent hydrosilylation of α-(fluoroalkyl)styrenes without defluorination

Dachang Bai (), Kangbao Zhong, Lingna Chang, Yan Qiao, Fen Wu, Guiqing Xu and Junbiao Chang ()
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Dachang Bai: Henan Normal University, Pingyuan laboratory
Kangbao Zhong: Henan Normal University, Pingyuan laboratory
Lingna Chang: Henan Normal University, Pingyuan laboratory
Yan Qiao: Zhengzhou University
Fen Wu: Henan Normal University, Pingyuan laboratory
Guiqing Xu: Henan Normal University, Pingyuan laboratory
Junbiao Chang: Henan Normal University, Pingyuan laboratory

Nature Communications, 2024, vol. 15, issue 1, 1-12

Abstract: Abstract The fluoroalkyl-containing organic molecules are widely used in drug discovery and material science. Herein, we report ligand regulated nickel(0)-catalyzed regiodivergent hydrosilylation of α-(fluoroalkyl)styrenes without defluorination, providing an atom- and step-economical synthesis route of two types of fluoroalkyl substituted silanes with exclusive regioselectivity. The anti-Markovnikov addition products (β-fluoroalkyl substituted silanes) are formed with monodentate phosphine ligand. Noteworthy, the bidentate phosphine ligand promote the generation of the more challenging Markovnikov products (α-fluoroalkyl substituted silanes) with tetrasubstituted saturated carbon centers. This protocol features with easy available starting materials and commercially available nickel catalysis, a wide range of substrates and excellent regioselectivity. The structure divergent products undergo a variety of transformations. Comprehensive mechanistic studies including the inverse kinetic isotope effects demonstrate the regioselectivity controlled by ligand structure through α-CF3 nickel intermediate. DFT calculations reveal a distinctive mechanism involving an open-shell singlet state, which is crucial for generating intricate tetra-substituted Markovnikov products.

Date: 2024
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DOI: 10.1038/s41467-024-50743-w

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