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

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 deuteriu...

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Bibliographic Details
Published in:Journal of organic chemistry 2022-01, Vol.87 (1), p.628-643
Main Authors: Borthakur, Ishani, Maji, Milan, Joshi, Abhisek, Kundu, Sabuj
Format: Article
Language:English
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Summary: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.
ISSN:0022-3263
1520-6904
DOI:10.1021/acs.joc.1c02625