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Rh(III)-Catalyzed Three-Component <i>Syn</i> -Carboamination of Alkenes Using Arylboronic Acids and Dioxazolones

Sumin Lee, Tomislav Rovis

2021ACS Catalysis65 citationsDOIOpen Access PDF

Abstract

Herein, we report a Rh(III)-catalyzed three-component carboamination of alkenes from readily available aryl boronic acids as a carbon source and dioxazolones as nitrogen electrophiles. This protocol provides facile access to valuable amine products including α-amino acid derivatives in good yield and regioselectivity without the need for a directing functionality. A series of experiments suggest a mechanism in which the Rh(III) catalyst undergoes transmetalation with the aryl boronic acid, followed by turnover limiting alkene migratory insertion into the Rh(III)-aryl bond. Subsequently, fast Rh-nitrene formation provides the syn-carboamination product selectively after reductive elimination and proto-demetalation. Importantly, the protocol provides three-component coupling products in preference to a variety of two-component undesired byproducts.

Topics & Concepts

CatalysisChemistryComponent (thermodynamics)AlkeneMedicinal chemistryOrganic chemistryCombinatorial chemistryThermodynamicsPhysicsCatalytic C–H Functionalization MethodsCatalytic Alkyne ReactionsCatalytic Cross-Coupling Reactions