Mechanistic Investigations of the Catalytic Formation of Lactams from Amines and Water with Liberation of H2

被引：52

作者：

Gellrich, Urs ^{[1
]}

Khusnutdinova, Julia R. ^{[1
]}

Leitus, Gregory M. ^{[2
]}

Milstein, David ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel

[2] Weizmann Inst Sci, Dept Chem Res Support, IL-76100 Rehovot, Israel

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 14期

基金：

以色列科学基金会; 欧洲研究理事会;

关键词：

CYCLIC AMINES; ALCOHOLS; OXIDATION; COMPLEX; AMIDES; ACTIVATION; CONVERSION;

D O I：

10.1021/jacs.5b01750

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The mechanism of the unique lactam formation from amines and water with concomitant H-2 liberation with no added oxidant, catalyzed by a well-defined acridine-based ruthenium pincer complex was investigated in detail by both experiment and DFT calculations. The results show that a dearomatized form of the initial complex is the active catalyst. Furthermore, reversible imine formation was shown to be part of the catalytic cycle. Water is not only the oxygen atom source but also acts as a cocatalyst for the H-2 liberation, enabled by conformational flexibility of the acridine-based pincer ligand.

引用

页码：4851 / 4859

页数：9

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