Litcius/Paper detail

Chan–Lam Amination of Secondary and Tertiary Benzylic Boronic Esters

James D. Grayson, Francesca M. Dennis, Craig C. Robertson, Benjamin M. Partridge

2021The Journal of Organic Chemistry43 citationsDOIOpen Access PDF

Abstract

We report a Chan-Lam coupling reaction of benzylic and allylic boronic esters with primary and secondary anilines to form valuable alkyl amine products. Both secondary and tertiary boronic esters can be used as coupling partners, with mono-alkylation of the aniline occurring selectively. This is a rare example of a transition-metal-mediated transformation of a tertiary alkylboron reagent. Initial investigation into the reaction mechanism suggests that transmetalation from B to Cu occurs through a single-electron, rather than a two-electron process.

Topics & Concepts

ChemistryTransmetalationAnilineAminationReagentTertiary amineAmine gas treatingOrganic chemistryAlkylAlkylationMedicinal chemistryCombinatorial chemistryCatalysisOrganoboron and organosilicon chemistryCatalytic Cross-Coupling ReactionsAsymmetric Hydrogenation and Catalysis