Issue 5, 2024
From the journal:

Chemical Science

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

Kaushik Chakrabarti,a   Michael M. Wade Wolfe,a   Shuo Guo, ORCID logo b   Joseph W. Tucker,c   Jisun Lee ORCID logo c  and  Nathaniel K. Szymczak ORCID logo *a  

* Corresponding authors

a Department of Chemistry, University of Michigan, 930 N. University, Ann Arbor, Michigan 48109, USA
E-mail: nszym@umich.edu

b College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, P.R. China

c Medicine Design, Pfizer Inc., Eastern Point Rd, Groton, CT, USA

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.

Graphical abstract: A metal-free strategy to construct fluoroalkyl–olefin linkages using fluoroalkanes

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Article information

DOI
https://doi.org/10.1039/D3SC05616C
Article type
Edge Article
Submitted
21 Oct 2023
Accepted
21 Dec 2023
First published
22 Dec 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2024,15, 1752-1757

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

K. Chakrabarti, M. M. Wade Wolfe, S. Guo, J. W. Tucker, J. Lee and N. K. Szymczak, Chem. Sci., 2024, 15, 1752 DOI: 10.1039/D3SC05616C

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