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Radical C−N Borylation of Aromatic Amines Enabled by a Pyrylium Reagent

Yuanhong Ma, Yue Pang, Sonia Chabbra, Edward J. Reijerse, Alexander Schnegg, Jan Niski, Markus Leutzsch, Josep Cornellà

2020Chemistry - A European Journal57 citationsDOIOpen Access PDF

Abstract

Abstract Herein, we report a radical borylation of aromatic amines through a homolytic C(sp 2 )−N bond cleavage. This method capitalizes on a simple and mild activation via a pyrylium reagent ( Sc Pyry‐OTf) thus priming the amino group for reactivity. The combination of terpyridine and a diboron reagent triggers a radical reaction which cleaves the C(sp 2 )−N bond and forges a new C(sp 2 )−B bond. The unique non‐planar structure of the pyridinium intermediate, provides the necessary driving force for the aryl radical formation. The method permits borylation of a wide variety of aromatic amines indistinctively of the electronic environment.

Topics & Concepts

BorylationChemistryReagentAryl radicalHomolysisPyridiniumBond cleavageArylMedicinal chemistryAromatic amineCombinatorial chemistryRadicalPhotochemistryOrganic chemistryCatalysisAlkylRadical Photochemical ReactionsCatalytic C–H Functionalization MethodsOrganoboron and organosilicon chemistry
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