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Download fileCatalytic Asymmetric Radical–Polar Crossover Hydroalkoxylation
journal contribution
posted on 25.10.2019, 13:42 authored by Christopher
A. Discolo, Eric E. Touney, Sergey V. ProninAsymmetric 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 may be involved in the enantiodetermining
step, where cation−π interactions in the catalyst contribute
to the asymmetric induction.