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A metal-free strategy to construct fluoroalkyl-olefin linkages using fluoroalkanes.

ABSTRACT: We present a metal-free strategy to access fluoroalkyl-olefin linkages from fluoroalkane precursors and vinyl-pinacol boronic ester (BPin) reagents. This reaction sequence is templated by the boron reagent, which induces C-C bond formation upon oxidation. We developed this strategy into a one-pot synthetic protocol using RCF₂H precursors directly with vinyl-BPin reagents in the presence of a Brønsted base, which tolerated oxygen- and nitrogen-containing heterocycles, and aryl halogens. We also found that HCF₃ (HCF-23; a byproduct of the Teflon industry) and CH₂F₂ (HCF-32; a low-cost refrigerant) are amenable to this protocol, representing distinct strategies to generate RCF₂H and RCF₃ molecules. Finally, we demonstrate that the vinyldifluoromethylene products can be readily derivatized, representing an avenue for late-stage modification after installing the fluoroalkyl unit.

SUBMITTER: Chakrabarti K

PROVIDER: S-EPMC10829021 | biostudies-literature | 2024 Jan

REPOSITORIES: biostudies-literature

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A metal-free strategy to construct fluoroalkyl-olefin linkages using fluoroalkanes.

Chakrabarti Kaushik K Wade Wolfe Michael M MM Guo Shuo S Tucker Joseph W JW Lee Jisun J Szymczak Nathaniel K NK

Chemical science 20231222 5

We present a metal-free strategy to access fluoroalkyl-olefin linkages from fluoroalkane precursors and vinyl-pinacol boronic ester (BPin) reagents. This reaction sequence is templated by the boron reagent, which induces C-C bond formation upon oxidation. We developed this strategy into a one-pot synthetic protocol using RCF<sub>2</sub>H precursors directly with vinyl-BPin reagents in the presence of a Brønsted base, which tolerated oxygen- and nitrogen-containing heterocycles, and aryl halogens ...[more]

PMID: 38303957

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