posted on 2020-03-08, 18:03authored byMichał Ociepa, Aleksandra J. Wierzba, Joanna Turkowska, Dorota Gryko
Strain-release-driven methodology
is a powerful tool for accessing
structural motifs, highly desirable by the pharmaceutical industry.
The reactivity of spring-loaded cyclic reagents is dominated by transformations
relying on their inherent electrophilic reactivity. Herein, we present
a polarity-reversal strategy based on light-driven cobalt catalysis,
which enables the generation of nucleophilic radicals through strain
release. The applicability of this methodology is demonstrated by
the design of two distinct types of reactions: Giese-type addition
and Co/Ni-catalyzed cross-coupling. Moreover, a series of electrochemical,
spectroscopic, and kinetic experiments as well as X-ray structural
analysis of the intermediate alkylcobalt(III) complex give deeper
insight into the mechanism of the reaction.