Issue 10, 2019

Dinuclear manganese alkoxide complexes as catalysts for C–N bond cleavage of simple tertiary N,N-dialkylamides to give esters

Abstract

Amide bonds are stable due to the resonance between the nitrogen lone pair and the carbonyl moiety, and therefore the chemical transformation of amides, especially tertiary amides, involving C–N bond fission is considered one of the most difficult organic reactions, unavoidably requiring harsh reaction conditions and strong acids or bases. We report the catalytic C–N bond cleavage of simple tertiary N,N-dialkylamides to give corresponding esters using a catalyst system (2 mol% based on Mn atoms) of a tetranuclear manganese alkoxide, [Mn(acac)(OEt)(EtOH)]4 (1c), combined with four equivalents of 4,7-bis(dimethylamino)-1,10-phenanthroline (L1: Me2N-Phen). Regarding the reaction mechanism, we isolated a dinuclear manganese complex, [Mn(acac)(OEt)(Phen)]2 (6c), which was revealed as the catalytically active species for the esterification of tertiary amides.

Graphical abstract: Dinuclear manganese alkoxide complexes as catalysts for C–N bond cleavage of simple tertiary N,N-dialkylamides to give esters

Supplementary files

Article information

Article type
Edge Article
Submitted
31 Dec. 2018
Accepted
28 Janv. 2019
First published
29 Janv. 2019
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2019,10, 2860-2868

Dinuclear manganese alkoxide complexes as catalysts for C–N bond cleavage of simple tertiary N,N-dialkylamides to give esters

H. Nagae, T. Hirai, D. Kato, S. Soma, S. Akebi and K. Mashima, Chem. Sci., 2019, 10, 2860 DOI: 10.1039/C8SC05819A

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