Facile and Fast Pinacol Rearrangement by AlCl3 in the Solid State.docVIP

Molecules 2001, 6, 442-447 molecules ISSN 1420-3049 Facile and Fast Pinacol Rearrangement by AlCl3 in the Solid State Parviz Rashidi-Ranjbar* and Ebrahim Kianmehr Department of Chemistry Tehran University, Box 14155-6455, Tehran, Iran. Tel. (+98)-021-6113301, Fax (+98)-021-6405141. * Author to whom correspondence should be addressed; e-mail Ranjbar@khayam.ut.ac.ir Received: 12 February 2000; in revised form 9 April 2001 / Accepted: 10 April 2001 / Published: 30 April 2001 Abstract: A facile and efficient synthetic procedure for effecting the pinacol rearrangement catalyzed by AlCl3 in the absence of solvent is developed. The rearrangement product is obtained at room temperature in a few minutes and in almost quantitative yield. Benzylic pinacols rearrange under these conditions, while aliphatic pinacols do not react. Keywords: Pinacol rearrangement, Solid state reactions, AlCl3, Lewis acid Introduction Organic reactions are found to occur efficiently in the solid state and many examples have been reported so far [1-5]. The pinacol rearrangement is usually carried out under drastic conditions, like heating in H2SO4. Toda found that the reaction proceeds faster and more selectively in the solid state by using organic acids like CCl3CO2H and p-TsOH [6]. It is possible to use a strong Lewis acid for the pinacol rearrangement and to the best of our knowledge, there has been no report on pinacol rearrangement by using a Lewis acid like AlCl3. This reagent has previously been used for Friedel- Crafts alkylation and acylation in the solid state [7] and also in Beckman rearrangements [8] under similar conditions. The novel utility of aluminium chloride as an efficient reagent for pinacol rearrangement is reported in this paper.  Molecules 2001, 6 443 Results and Discussion Benzylic pinacols react with AlCl3 to give the corresponding rearrangement product in almost quantitative yie