Reversal of Regioselectivity in Reactions of Donor-Acceptor Cyclopropanes with Eelectrophilic Olefins

13 September 2021, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Cyclopropanes bearing donor and acceptor groups at the opposite ends of the C-C bond should react with both nucleophiles and electrophiles. Their reactivity towards nucleophiles is well explored while only few specific electrophilic reagents give desired products.These methods are limited by the specific philicity of the carbon atoms resulting from the strong polarization of the central C-C bond. Herein, we report that vitamin B12 catalysis enables the transformation of initially electrophilic center into a nucleophilic radical that as such reacts with SOMOphiles. This radical-based strategy reverses the standard regioselectivity and thus complements the classical approaches.

Keywords

cobalamins
Co-catalysis
cyclopropanes
•donor-acceptor systems
ring opening

Supplementary materials

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Description
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Title
Reversal of Regioselectivity in Reactions of Donor-Acceptor Cyclopropanes with Eelectrophilic Olefins
Description
Experimental details and procedures, optimization studies, mechanistic experiments, and spectral data for all new compounds are given.
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