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Molecules 2006, 11, 421-434 molecules ISSN 1420-3049 Review Hypervalent Iodine–Mediated Ring Contraction Reactions Luiz F. Silva, Jr* Instituto de Química, Universidade de São Paulo, CP 26077, CEP 05513-970, São Paulo SP, Brazil; Tel. (+55)-11-3091-2388, Fax (+55)-11-3815-5579 * Author to whom correspondence should be addressed; e-mail: luizfsjr@iq.usp.br Received: 27 November 2005 / Accepted: 2 May 2006 / Published: 20 June 2006 Abstract: Hypervalent iodine reagents constitute a powerful tool in modern synthetic organic chemistry, promoting several important reactions. One such reaction is the ring contraction of cycloalkenes and cycloalkanones promoted by iodine(III) compounds, such as iodobenzene diacetate, iodosylbenzene, iodotoluene difluoride, and [hydroxy(tosyloxy)- iodo]benzene (Koser´s reagent). This review covers all the literature related to the ring contraction of cyclic ketones and olefins promoted by iodine(III) species. Keywords: Iodine(III), hypervalent iodine, ring contraction, oxidation, cycloalkenes, cycloalkanones. Introduction Ring contraction reactions are an important method to increase molecular complexity in a single step, because, in several cases, the reorganization of the bonds occurs with a high level of selectivity, affording products not easily accessible by other approaches [1]. Ring contraction reactions can be effected by acids, by bases, by oxidizers or photochemically [1]. Among the oxidizers, one of the most used is thallium trinitrate (TTN) [2, 3]. In the