A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins

The first catalytic intermolecular 1,2-alkylborylation reaction via a radical-relay mechanism between unactivated olefins, bis­(pinacolato)­diboron, and an alkyl electrophile is reported. Successful implementation of this method requires that the competing boryl substitution of the alkyl electrophil...

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Bibliographic Details
Published in:Journal of the American Chemical Society 2021-04, Vol.143 (13), p.5260-5268
Main Authors: Akiyama, Sota, Oyama, Natsuki, Endo, Tsubura, Kubota, Koji, Ito, Hajime
Format: Article
Language:English
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Summary:The first catalytic intermolecular 1,2-alkylborylation reaction via a radical-relay mechanism between unactivated olefins, bis­(pinacolato)­diboron, and an alkyl electrophile is reported. Successful implementation of this method requires that the competing boryl substitution of the alkyl electrophile is retarded to facilitate the radical relay. This challenge was overcome using electronically or sterically demanding alkyl electrophiles, which results in the simultaneous and highly regioselective introduction of a gem-difluoro, monofluoro, tertiary, or secondary alkyl group and a boryl group across the CC double bond.
ISSN:0002-7863
1520-5126
DOI:10.1021/jacs.1c02050