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 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.

Automated summary

The first catalytic intermolecular 1,2-alkylborylation reaction via a radical-relay mechanism was reported in this study, involving unactivated olefins, bis(pinacolato)diboron, and an alkyl electrophile. Overcoming the challenge of competing boryl substitution of the alkyl electrophile was achieved by using electronically or sterically demanding alkyl electrophiles, resulting in the simultaneous and highly regioselective introduction of various alkyl and boron groups.