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

Sota Akiyama, Natsuki Oyama, Tsubura Endo, Koji Kubota, Hajime Ito

2021Journal of the American Chemical Society45 citationsDOIOpen Access PDF

Abstract

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.

Topics & Concepts

ChemistryElectrophileRegioselectivityAlkylSteric effectsIntermolecular forceCatalysisRelayReagentMedicinal chemistryPhotochemistryCombinatorial chemistryOrganic chemistryMoleculePhysicsPower (physics)Quantum mechanicsFluorine in Organic ChemistryRadical Photochemical ReactionsOrganoboron and organosilicon chemistry
A Copper(I)-Catalyzed Radical-Relay Reaction Enabling the Intermolecular 1,2-Alkylborylation of Unactivated Olefins | Litcius