Aerobic Oxidation of Pinacol by Vanadium(V) Dipicolinate Complexes: Evidence for Reduction to Vanadium(III)

被引：99

作者：

Hanson, Susan K. ^{[1
]}

Baker, R. Tom ^{[1
]}

Gordon, John C. ^{[1
]}

Scott, Brian L. ^{[2
]}

Sutton, Andrew D. ^{[1
]}

Thorn, David L. ^{[3
]}

机构：

[1] Los Alamos Natl Lab, Div Chem, Los Alamos, NM 87545 USA

[2] Los Alamos Natl Lab, Mat Phys Applicat Div, Los Alamos, NM 87545 USA

[3] Los Alamos Natl Lab, Chem Life & Earth Sci Directorate, Los Alamos, NM 87545 USA

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2009年 / 131卷 / 02期

关键词：

ALPHA-HYDROXY ESTERS; QUINQUEVALENT VANADIUM; VIC-DIOLS; ORGANIC COMPOUNDS; BOND-CLEAVAGE; IONIC LIQUIDS; ALCOHOLS; CELLULOSE; ALDEHYDES; BIOMASS;

D O I：

10.1021/ja807522n

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The reactivity of vanadium complexes bearing the ligand dipicolinic acid (H(2)dipic) with alcohols has been explored. Dipic vanadium complexes are able to catalyze the aerobic oxidative C-C bond cleavage of pinacol. Reaction under anaerobic conditions allowed for isolation of a V-III mu-oxo dimer, supporting the involvement of V-III in aerobic oxidation reactions. Stoichiometric oxidation of unactivated aliphatic alcohols has also been observed, with oxidation of cyctobutanot producing cyclobutanone in 93% yield. The absence of ring-opening products in this reaction provides further support for the involvement of V-III intermediates.

引用

页码：428 / +

页数：3

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