Catalyst- and Silane- Controlled Enantioselective Hydrofunctionalization of Alkenes by Cobalt-Catalyzed Hydrogen Atom Transfer and Radical-Polar Crossover

07 May 2020, Version 2
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

Catalytic enantioselective synthesis of tetrahydrofurans, which are found in the structures of many biologically active natural products, via a transition-metal catalyzed-hydrogen atom transfer (TM-HAT) and radical-polar crossover (RPC) mechanism is described herein. Hydroalkoxylation of non-conjugated alkenes proceeded efficiently with excellent enantioselectivity (up to 94% ee) using a suitable chiral cobalt catalyst, N-fluoro-2,4,6-collidinium tetrafluoroborate, and diethylsilane. Surprisingly, absolute configuration of the product was highly dependent on the steric hindrance of the silane. Slow addition of the silane, the dioxygen effect in the solvent, thermal dependency, and DFT calculation results supported the unprecedented scenario of two competing selective mechanisms. For the less-hindered diethylsilane, a high concentration of diffused carbon-centered radicals invoked diastereoenrichment of an alkylcobalt(III) intermediate by a radical chain reaction, which eventually determined the absolute configuration of the product. On the other hand, a more hindered silane resulted in less opportunity for radical chain reaction, instead facilitating enantioselective kinetic resolution during the late-stage nucleophilic displacement of the alkylcobalt(IV) intermediate.

Keywords

hydrogen atom transfer
radical-polar crossover reactions
cobalt catalyst
hydrofunctionalization
Enantioselective reaction

Supplementary materials

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2020Co enantio SI
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2020Co enantio SI2
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