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

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• 作者：Susan K. Hanson ; R. Tom Baker ; John C. Gordon ; Brian L. Scott ; Andrew D. Sutton ; David L. Thorn
• 刊名：Journal of the American Chemical Society
• 出版年：2009
• 出版时间：January 21, 2009
• 年：2009
• 卷：131
• 期：2
• 页码：428-429
• 全文大小：125K
• 年卷期：v.131,no.2(January 21, 2009)
• ISSN：1520-5126

文摘

The reactivity of vanadium complexes bearing the ligand dipicolinic acid (H₂dipic) 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 μ-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 cyclobutanol producing cyclobutanone in 93% yield. The absence of ring-opening products in this reaction provides further support for the involvement of V^III intermediates.