Organometallic Chemistry

The Stabilizing Effect of Pre-Equilibria: A Trifluoromethyl Complex as CF2 Reservoir in Catalytic Olefin Difluorocarbenation

Jakub Hyvl University of Hawai‘i at Mānoa

Abstract

A new, efficient, catalytic difluorocarbenation of olefins to give 1,1-difluorocyclopropanes is presented. The catalyst, an organobismuth complex, uses TMSCF3 as a stoichiometric difluorocarbene source. We demonstrate both the viability and robustness of this reaction over a wide range of alkenes and alkynes, including electron-poor alkenes, to generate the corresponding 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes. Ease of catalyst recovery from the reaction mixture is another attractive feature of this method. In depth experimental and theoretical studies showed that the key difluorocarbene-generating step proceeds through a bismuth non-redox synchronous mechanism generating a highly reactive free CF2 in an endergonic pre-equilibrium. It is the reversibility when generating the difluorocarbene that accounts for the high selectivity, while minimizing CF2-recombination side-reactions.

Content

Thumbnail image of Hyvl_BiCF3_Manuscript_revised.pdf
download asset Hyvl_BiCF3_Manuscript_revised.pdf 1 MB [opens in a new tab]

Supplementary material

Thumbnail image of Hyvl_BiCF3_SI.pdf
download asset Hyvl_BiCF3_SI.pdf 3 MB [opens in a new tab]
Hyvl BiCF3 SI

Supplementary weblinks