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双核锰醇盐配合物作为简单叔二烷基酰胺碳氮键断裂制备酯的催化剂。

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

作者信息

Nagae Haruki, Hirai Takahiro, Kato Daiki, Soma Shusei, Akebi Shin-Ya, Mashima Kazushi

机构信息

Department of Chemistry , Graduate School of Engineering Science , Osaka University , Toyonaka , Osaka 560-8531 , Japan . Email:

出版信息

Chem Sci. 2019 Jan 29;10(10):2860-2868. doi: 10.1039/c8sc05819a. eCollection 2019 Mar 14.

DOI:10.1039/c8sc05819a
PMID:30996863
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6429592/
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 ,-dialkylamides to give corresponding esters using a catalyst system (2 mol% based on Mn atoms) of a tetranuclear manganese alkoxide, [Mn(acac)(OEt)(EtOH)] (), combined with four equivalents of 4,7-bis(dimethylamino)-1,10-phenanthroline (: MeN-Phen). Regarding the reaction mechanism, we isolated a dinuclear manganese complex, [Mn(acac)(OEt)(Phen)] (), which was revealed as the catalytically active species for the esterification of tertiary amides.

摘要

由于氮孤对与羰基部分之间的共振，酰胺键是稳定的，因此涉及C-N键断裂的酰胺，尤其是叔酰胺的化学转化被认为是最困难的有机反应之一，不可避免地需要苛刻的反应条件以及强酸或强碱。我们报道了使用四核锰醇盐Mn(acac)(OEt)(EtOH)与四当量的4,7-双（二甲基氨基）-1,10-菲咯啉（：MeN-Phen）组成的催化剂体系（基于锰原子为2 mol%），将简单的叔α，α-二烷基酰胺进行催化C-N键裂解以得到相应的酯。关于反应机理，我们分离出了双核锰配合物Mn(acac)(OEt)(Phen)，它被证明是叔酰胺酯化反应的催化活性物种。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/e7563135f522/c8sc05819a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/712cc4ffcc0f/c8sc05819a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/73e2cdffdc96/c8sc05819a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/8691bb3ff4c6/c8sc05819a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/b633f0012e3f/c8sc05819a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/e7563135f522/c8sc05819a-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/712cc4ffcc0f/c8sc05819a-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/73e2cdffdc96/c8sc05819a-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/8691bb3ff4c6/c8sc05819a-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/b633f0012e3f/c8sc05819a-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ff01/6429592/e7563135f522/c8sc05819a-s1.jpg

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