RT info:eu-repo/semantics/article T1 Prins Cyclization Catalyzed by a FeIII/Trimethylsilyl Halide System: The Oxocarbenium Ion Pathway versus the [2+2] Cycloaddition A1 Pérez, Sixto J. A1 Purino, Martín A. A1 Miranda, Pedro O. A1 Martín, Víctor S. A1 Fernández, Israel A1 Padrón, Juan I. AB The different factors that control the alkene Prins cyclization catalyzed by iron(III) salts have been explored by means of a joint experimental¿computational study. The iron(III) salt/trimethylsilyl halide system has proved to be an excellent promoter in the synthesis of crossed all-cis disubstituted tetrahydropyrans, minimizing the formation of products derived from side-chain exchange. In this iron(III)-catalyzed Prins cyclization reaction between homoallylic alcohols and non-activated alkenes, two mechanistic pathways can be envisaged, namely the classical oxocarbenium route and the alternative [2+2] cycloaddition-based pathway. It is found that the [2+2] pathway is disfavored for those alcohols having non-activated and non-substituted alkenes. In these cases, the classical pathway, via the key oxocarbenium ion, is preferred. In addition, the final product distribution strongly depends upon the nature of the substituent adjacent to the hydroxy group in the homoallylic alcohol, which can favor or hamper a side 2-oxonia-Cope rearrangement. PB Wiley YR 2015 FD 2015 LK http://riull.ull.es/xmlui/handle/915/3741 UL http://riull.ull.es/xmlui/handle/915/3741 LA en NO Pérez, S. J., Purino, M., Miranda, P. O., Martín, V. S., Fernández, I. and Padrón, J. I. (2015), Prins Cyclization Catalyzed by a FeIII/Trimethylsilyl Halide System: The Oxocarbenium Ion Pathway versus the [2+2] Cycloaddition. Chem. Eur. J., 21: 15211¿15217. doi:10.1002/chem.201502488 NO Spanish MINECO, co-financed by the European Regional Development Fund (ERDF) and FEDER (CTQ2011-28417-C02¿01/BQU, CTQ2014-56362-C2¿1-P, CTQ2011-22653, CTQ2013-44303-P) and IMBRAIN project (FP7-REGPOT-2012-CT2012-31637-IMBRAIN), funded under the 7th Framework Programme (CAPACITIES) DS Repositorio institucional de la Universidad de La Laguna RD 25-abr-2024