The chemistry described herein involves the transformation of alkene and alkyne substrates into 1,1-difluorocyclopropanes and 1,1-difluorocyclopropenes, respectively, by a novel catalytic process.[1] A series of hypervalent trifluoromethyl bismuth complexes are outlined that, in an atom-economical and waste minimal way, generate these fluorohydrocarbons, which are valuable substances with potential applications in agrochemical, materials, and the pharmaceutical industries. The catalytic process in the scheme above was recently discovered by us and we hope to capitalized on this promising means to fluorinate olefins and alkynes via carbene addition reactions. Our preliminary results indicate that this transformation can be applied to a variety of alkenes, styrene and methylstyrene, for example, as well as relatively electron-poor substrates such as stilbene and cinnamate esters. These electron-poor substrates are particularly valuable, since their respective products are difficult to obtain by standard protocols relying on formation of a free difluorocarbene. Furthermore, our work includes a second emphasis involving a careful investigation of the reaction mechanism by experimental and theoretical means, and this will be also discussed in due time.

Difluorocarbenation of alkene and alkyne substrates catalyzed by hypervalent bismuth complexes

ACS Spring 2022

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