Regioselective Markovnikov hydrodifluoroalkylation of alkenes using difluoroenoxysilanes

Xiao-Si Hu, Jun-Xiong He, Su-Zhen Dong, Qiu-Hua Zhao, Jin-Sheng Yu () and Jian Zhou ()
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Xiao-Si Hu: East China Normal University
Jun-Xiong He: East China Normal University
Su-Zhen Dong: East China Normal University
Qiu-Hua Zhao: East China Normal University
Jin-Sheng Yu: East China Normal University
Jian Zhou: East China Normal University

Nature Communications, 2020, vol. 11, issue 1, 1-9

Abstract: Abstract Alkene hydrodifluoroalkylation is a fruitful strategy for synthesizing difluoromethylated compounds that are interesting for developing new medicinal agents, agrochemicals, and advanced materials. Whereas the anti-Markovnikov hydrodifluoroalkylation to linear-type products is developed, employing radical-based processes, the Markovnikov synthesis of branched adducts remains unexplored. Herein, we describe acid-catalyzed processes involving carbocation intermediates as a promising strategy to secure the Markovnikov regioselectivity. Accordingly, the Markovnikov hydrodifluoroalkylation of mono-, di-, tri-, and tetrasubstituted alkenes using difluoroenoxysilanes, catalyzed by Mg(ClO4)2·6H2O, is achieved. This allows the diversity-oriented synthesis of α,α-difluoroketones with a quaternary or tertiary carbon at the β-position that are otherwise difficult to access. The method is applied to the modification of natural products and drug derivatives. The resulting α,α-difluorinated ketones could be converted to the corresponding α,α-difluorinated esters or alcohols, or organofluorine compounds featuring a CF2H or CF2CF2Ph moiety. Mechanistic studies support that Mg(ClO4)2·6H2O functions as a hidden Brønsted acid catalyst.

Date: 2020
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DOI: 10.1038/s41467-020-19387-4

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