ElectronTransfer Induced Ring Opening of α-Epoxyketones Spirodioxolane Formation.docVIP

Molecules 2002, 7, 63-71 molecules ISSN 1420-3049 ElectronTransfer Induced Ring Opening of α-Epoxyketones: Spirodioxolane Formation Hamid R. Memarian and Farzad Nikpour * University of Isfahan, Faculty of Sciences, Department of Chemistry, 81744 Isfahan, Iran. Tel: (+98) 311-793 2707, Fax: (+98) 311-668 9732. * Author to whom correspondence should be addressed, e-mail: memarian@sci.ui.ac.ir Received: 21 July 2001; in revised form: 17 November 2001 / Accepted: 13 December 2001 / Published: 31 January 2002 Abstract: Stereospecific formation of spirodioxolanes has been observed on electron of α-epoxyketones by 2,4,6-triphenylpyrylium tetrafluoroborate in the presence of cyclohexanone. transfer induced ring opening Keywords: Dioxolanes; Electron transfer; α-Epoxyketones; Photochemistry; Spiro compounds. Introduction Ring opening of epoxides and α-epoxyketones induced by electron transfer to suitable electron acceptors in the presence of various nucleophiles leads to the formation of some interesting compounds such as ethers, dioxolanes and trioxolanes. Such reactions have been recognized as important processes not only in thermal but also in photochemical reactions. Single electron transfer (SET) induced ring opening reactions of epoxides [1-4], α-epoxyketones [5-8] and α-epoxyesters [9] have demonstrated Cα-Cβ, Cα-O and Cβ-O bond cleavage through photosensitized electron transfer by dicyanoanthracene [1,2], tetracyanoethylene [3,4] and 2,4,6- triphenylpyrylium tetrafluoroborate [5-8] or thermally induced electron transfer to ceric ammonium nitrate [10,11], 2,3-dichloro-5,6-dicyano-p-benzoquinone [12] and iron (III) chloride [13].  Molecules 2002, 7 64 Previously we investigated the formation of charge-transfer complexes between some α-epoxy- ketones as donor molecules and tetracyanoethylene (TCNE) as the acceptor molecule [14]. These