Nitrous Oxide as a Hydrogen Acceptor for the Dehydrogenative Coupling of Alcohols

被引：75

作者：

Gianetti, Thomas L. ^{[1
]}

Annen, Samuel P. ^{[1
]}

Santiso-Quinones, Gustavo ^{[1
]}

Reiher, Markus ^{[2
]}

Driess, Matthias ^{[3
]}

Gruetzmacher, Hansjoerg ^{[1
]}

机构：

[1] ETH, Dept Chem & Appl Biosci, Inorgan Chem Lab, Wolfgang Pauli Str 10, CH-8093 Zurich, Switzerland

[2] ETH, Dept Chem & Appl Biosci, Phys Chem Lab, Wolfgang Pauli Str 10, CH-8093 Zurich, Switzerland

[3] Tech Univ Berlin, Inst Chem Metalorgan & Inorgan Mat, Str 17 Juni 135, D-10623 Berlin, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2016年 / 55卷 / 05期

基金：

瑞士国家科学基金会;

关键词：

alcohols; catalysis; coupling reactions; dehydrogenation; nitrous oxide; rhodium; OXYGEN-ATOM TRANSFER; GENERALIZED GRADIENT APPROXIMATION; 3-COORDINATE MOLYBDENUM(III); CATALYTIC DECOMPOSITION; N2O DECOMPOSITION; REACTIVITY; COMPLEXES; WATER; BOND; CONVERSION;

D O I：

10.1002/anie.201509288

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The oxidation of alcohols with N2O as the hydrogen acceptor was achieved with low catalyst loadings of a rhodium complex that features a cooperative bis(olefin) amido ligand under mild conditions. Two different methods enable the formation of either the corresponding carboxylic acid or the ester. N-2 and water are the only by-products. Mechanistic studies supported by DFT calculations suggest that the oxygen atom of N2O is transferred to the metal center by insertion into the Rh-H bond of a rhodium amino hydride species, generating a rhodium hydroxy complex as a key intermediate.

引用

页码：1854 / 1858

页数：5

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