Self-Terminating, Oxidative Radical Cyclizations 英文参考文献.docVIP

Molecules 2004, 9, 480–497 molecules ISSN 1420-3049 Self-Terminating, Oxidative Radical Cyclizations Tim Dreessen , Christian Jargstorff , Lars Lietzau , Christian Plath , Arne Stademann and 2 2 2 2 2 1, Uta Wille * 1 School of Chemistry, The University of Melbourne, Victoria 3010, Australia. Tel. (+61) 3 8344 7622, Fax (+61) 3 9347 5180, e-mail uwille@.au. 2 Institut für Organische Chemie, Universit?t Kiel, Olshausenstr. 40, 24098 Kiel, Germany. Received: 23 February 2004 / Accepted: 1 March 2004 / Published: 31 May 2004 Abstract: The recently discovered novel concept of self-terminating, oxidative radical cyclizations, through which alkynes can be converted into carbonyl compounds under very mild reaction conditions using O-centered inorganic and organic radicals as oxidants, is described Keywords: Radical reactions, O-centered radicals, cyclizations, oxidations. Introduction During the past 20–30 years radical reactions became an important synthetic tool, especially for the synthesis of complicated, often polycyclic molecules. The success of this methodology is a result of (i) the mostly excellent stereoselectivities of these reactions [1], and (ii) the downright ease of radical generation and radical chain maintaining by using the combination of alkyl halides (or thiols, selenides, nitro compounds, etc.) with transition metal or non-metal hydrides (generally tin, mercury or silicon compounds) as radical precursors [2,3]. However, this advantage can turn into a serious disadvantage, if the difficulty to remove the toxic tin or mercury compounds from the reaction mixture is considered. The demand for non-toxic alternatives is therefore steadily increasing, and meanwhile many interesting new concept