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Theoretical study on the BF3-catalyzed meinwald rearrangement reaction

AutorFraile, José M. ; Mayoral, José A. ; Salvatella, Luis
Fecha de publicación2014
EditorAmerican Chemical Society
CitaciónJournal of Organic Chemistry 79(13): 5993-5999 (2014)
ResumenThe mechanisms of the BF3-catalyzed Meinwald rearrangement reactions of five epoxides in dichloromethane solution have been studied at the M062X/6-311++G(2df,2pd) level. Accordingly, the Lewis acid-epoxide complex can react through several alternative pathways, though three phases (ring opening, C-C bond rotation, and hydrogen or alkyl group migration) are required in any path. In some cases, a concerted pathway (involving all three successive phases) is found. Otherwise, the reaction takes place through a reaction mechanism involving a zwitterion or a BF3 addition compound (formed by fluoride transfer from the BF3 moiety to the incipient carbocationic center generated by C-O bond rupture) or both as reaction intermediate(s). The BF 2-bound fluorohydrin yields the reaction product through a concerted process involving fluoride transfer from the C-F bond to the OBF2 group and hydrogen or alkyl group migration, as first demonstrated in this work. Effects of a number of features (solvent effects, concurrent hydrogen/alkyl group migration, carbocation substitution, benzylic conjugation) are also discussed. © 2014 American Chemical Society.
URIhttp://hdl.handle.net/10261/111787
DOI10.1021/jo5003888
Identificadoresdoi: 10.1021/jo5003888
issn: 0022-3263
e-issn: 1520-6904
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