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

preprint
revised on 29.01.2021, 07:02 and posted on 01.02.2021, 06:10 by Thomas Louis-Goff, Huu Vinh Trinh, Eileen Chen, Arnold L. Rheingold, Christian Ehm, Jakub Hyvl
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.

Funding

University of Hawaii at Manoa - start-up funds

History

Email Address of Submitting Author

hyvl@hawaii.edu

Institution

University of Hawai‘i at Mānoa

Country

United States

ORCID For Submitting Author

0000-0002-5509-5567

Declaration of Conflict of Interest

A provisional patent on this work, application no. 63/122,374, has been filed by University of Hawai‘i.

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