Epoxidation vs. dehydrogenation of allylic alcohols: heterogenization of the VO(acac)(2) catalyst in a metal-organic framework

[EN] Allylic alcohol epoxidation and dehydrogenation reactivity is distinguished when VO(acac)(2) is used in solution or anchored in a metal-organic framework (MOF). The chemical mechanism depends on the electronic profile of alkene substituents when the vanadyl complex is used in the homogenous phase. However, confinement effects imparted by MOF channels allow gaining control of the chemoselectivity toward the dehydrogenation product. We acknowledge MCIN (PID2019-104778GB-I00, PID2020115100GB-I00 and CEX2019-000919-M), the Generalitat Valenciana (SEJI/2020/034 and PROMETEO/2021/054), the Ministero dell'Istruzione, dell'Universitae della Ricerca, the Fondazione CARIPLO (2019-2090) and the European Research Council (814804, MOFreactors). J. O.-M. and C. B. thank the Juan de la Cierva program (IJC2018-036514-I) and ITQ, respectively, for contracts. J. F.-S. thanks Ramon y Cajal program (RYC2019-027940-I). Negro, C.; Bilanin-Artigado, C.; Qu, X.; Oliver-Meseguer, J.; Ferrando-Soria, J.; Leyva Perez, A.; Armentano, D... (2022). Epoxidation vs. dehydrogenation of allylic alcohols: heterogenization of the VO(acac)(2) catalyst in a metal-organic framework. Chemical Communications. 58(37):5578-5581. https://doi.org/10.1039/d2cc01137a