Manganese-Catalyzed Aminomethylation of Aromatic Compounds with Methanol as a Sustainable C1 Building Block

被引：160
|
作者：
Mastalir, Matthias [1 ]
Pittenauer, Ernst [2 ]
Allmaier, Guenter [2 ]
Kirchner, Karl [1 ]
机构：
[1] Vienna Univ Technol, Inst Appl Synthet Chem, Getreidemarkt 9, A-1060 Vienna, Austria
[2] Vienna Univ Technol, Inst Chem Technol & Analyt, Getreidemarkt 9, A-1060 Vienna, Austria
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2017年 / 139卷 / 26期
基金：
奥地利科学基金会;
关键词：
ALPHA-ALKYLATION; BOND FORMATION; N-METHYLATION; ALCOHOLS; AMINES; HYDROGENATION; DEHYDROGENATION; KETONES; LIGAND; ESTERS;
D O I：
10.1021/jacs.7b05253
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
This study represents the first example of a manganese-catalyzed environmentally benign, practical three-component aminomethylation of activated aromatic compounds including naphtols, phenols, pyridines, in doles, carbazoles, and thiophenes in combination with amines and MeOH as a Cl source. These reactions proceed with high atom efficiency via a sequence of dehydrogenation and condensation steps which give rise to selective C-C and C-N bond formations, thereby releasing hydrogen and water. A well-defined hydride Mn(I) PNP pincer complex, recently developed in our laboratory, catalyzes this process in a very efficient way, and a total of 28 different aminomethylated products were synthesized and isolated yields of up to 91%. In a preliminary study, a related Fe(II) PNP pincer complex was shown to catalyze the methylation of 2-naphtol rather than its aminomethylation displaying again the divergent behavior of isoelectronic Mn(I) and Fe(II) PNP pincer systems.
引用
收藏
页码：8812 / 8815
页数：4
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