DOI: 10.1002/adsc.200600397 Vanadium-Catalyzed Selective Oxidation of Alcohols to Aldehydes and Ketones with tert-Butyl Hydroperoxide Laxmidhar Rout, a Pinku Nath, a and Tharmalingam Punniyamurthy a, * a Department of Chemistry, Indian Institute of Technology Guwahati, Guwahati 781039, India Fax:(+ 91)-361-2690762; e-mail: tpunni@iitg.ernet.in Received: August 7, 2006 Supporting information for this article is available on the WWW under http://asc.wiley-vch.de/home/. Abstract: The oxidation of alcohols to aldehydes and ketones has been described using silica-sup- ported vanadium(IV) oxide (V/SiO 2 , 1) in the pres- ence of tert-butyl hydroperoxide in tert-butyl alco- hol at ambient temperature with quantitative yields. The procedure is simple, efficient and environmen- tally benign. Keywords: alcohols; tert-butyl hydroperoxide; cata- lyst; oxidation; vanadium The oxidation of alcohols to aldehydes and ketones is one of the fundamental processes in organic synthe- sis. [1,2] The traditional methods for this purpose usual- ly employ stoichiometric quantities of inorganic re- agents such as chromate and permanganate, which often generate significant amount of inorganic salt- containing effluent along with the target molecules. [3] Removal of traces of these effluents from the reaction mixture is often difficult and demands laborious work-up procedures. To circumvent this problem, much attention has been recently focused on the design and development of catalytic systems, especial- ly without reducing agents in ecologically benign con- ditions to reduce the environmental impact of the process (E factor). [4–13] During the course of our inves- tigation on the oxidation of organic compounds, [13] we found that the silica-supported vanadium(IV) oxide 1 catalyzed efficiently the oxidation of heteroatoms with 30% H 2 O 2 in high yields. [14] Since the catalyst 1 is readily accessible, cheap and provides simplified product isolation, we wanted to further explore its ap- plication to other reactions. In this contribution, we report the oxidation of alcohols to aldehydes and ke- tones in the presence of tert-butyl hydroperoxide (t- BuOOH) in tert-butyl alcohol (t-BuOH) at ambient temperature (Scheme 1). It is a clean technological process and no additive is involved. Since the reac- tions usually take place with 100% conversion, after filtering the catalyst 1, the filtrate could be evaporat- ed to provide the aldehydes or ketones as the only products. The oxidation of p-anisyl alcohol was first studied as a standard substrate using 1 in the presence of t- BuOOH at ambient temperature (Table1). We were pleased to find that the reaction occurred to afford p- anisaldehyde in quantitative yield when it was al- lowed to stir with 15 mg of 1 (5 mol% V) and 1.2equivs. of t-BuOOH (5 M in decane) for 3 h in t- Scheme 1. Table 1. Oxidation of anisyl alcohol. [a] [a] Substrate (1 mmol), ROOH (1.2 mmol) and catalyst 1 (15 mg, 5 mol% V) were stirred in t-BuOH (1 mL) at ambient temperature for 3 h. [b] R = p-MeOC 6 H 4 -. [c] t-BuOOH was consumed in 1 h. 846 # 2007 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim Adv. Synth. Catal. 2007, 349,846–848 COMMUNICATIONS