Catalytic Asymmetric Radical-Polar Crossover Hydroalkoxylation

23 October 2019, Version 2
This content is a preprint and has not undergone peer review at the time of posting.


Asymmetric intramolecular hydrofunctionalization of tertiary allylic alcohols is described. This metal hydride-mediated catalytic radical-polar crossover reaction delivers corresponding epoxides in good to high enantioselectivity and constitutes the first example of asymmetric hydrogen atom transfer-initiated process. A series of modified cobalt salen complexes has proven optimal for achieving good efficiency and asymmetric induction. Experimental data suggest that cationic cobalt complexes are involved in enantio-determining step, where cation–π interactions in the catalyst contribute to the asymmetric induction.


enantioselective hydrofunctionalization
Markovnikov selectivity
radical reactions
hydrogen atom transfer
radical-polar crossover reactions
cobalt catalysis
cobalt salen complexes

Supplementary materials

Supporting Information Pronin et al revised


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