Litcius/Paper detail

Reductive Alkylation of Azides and Nitroarenes with Alcohols: A Selective Route to Mono- and Dialkylated Amines

Ishani Borthakur, Milan Maji, Abhisek Joshi, Sabuj Kundu

2021The Journal of Organic Chemistry18 citationsDOI

Abstract

Herein, we demonstrated an efficient protocol for reductive alkylation of azides/nitro compounds via a borrowing hydrogen (BH) method. By following this protocol, selective mono- and dialkylated amines were obtained under mild and solvent-free conditions. A series of control experiments and deuterium-labeling experiments were performed to understand this catalytic process. Mechanistic studies suggested that the Ir(III)-H was the active intermediate in this reaction. KIE study revealed that the breaking of the C-H bond of alcohol might be the rate-limiting step. Notably, this solvent-free strategy disclosed a high TON of around 5600. Based on kinetic studies and control experiments, a metal-ligand cooperative mechanism was proposed.

Topics & Concepts

ChemistryAlkylationCatalysisAlcoholCombinatorial chemistrySolventNitroDeuteriumOrganic chemistryAlkylQuantum mechanicsPhysicsAsymmetric Hydrogenation and CatalysisNanomaterials for catalytic reactionsChemical Synthesis and Analysis