Theoretical study on the BF3-catalyzed meinwald rearrangement reaction

The 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.Financial support from the Ministerio de Ciencia e Innovación (MICINN/FEDER) of Spain (Project CTQ2011-28124) and the Gobierno de Aragón (Group E11) is gratefully acknowledged.Peer Reviewe

Measurement of the lifetimes of promptly produced Ωc0Ω^{0}_{c} and Ξc0Ξ^{0}_{c} baryons

A measurement of the lifetimes of the $\Omega^{0}_{c}$ and $\Xi^{0}_{c}$ baryons is reported using proton-proton collision data at a centre-of-mass energy of $13\text{ TeV}$, corresponding to an integrated luminosity of $5.4\text{ fb}^{-1}$ collected by the LHCb experiment. The $\Omega^{0}_{c}$ and $\Xi^{0}_{c}$ baryons are produced directly from proton interactions and reconstructed in the $pK^{-}K^{-}\pi^{+}$ final state. The $\Omega^{0}_{c}$ lifetime is measured to be $276.5\pm13.4\pm4.4\pm0.7\text{ fs}$, and the $\Xi^{0}_{c}$ lifetime is measured to be $148.0\pm2.3\pm2.2\pm0.2\text{ fs}$, where the first uncertainty is statistical, the second systematic, and the third due to the uncertainty on the $D^{0}$ lifetime. These results confirm previous LHCb measurements based on semileptonic beauty-hadron decays, which disagree with earlier results of a four times shorter $\Omega^{0}_{c}$ lifetime, and provide the single most precise measurement of the $\Omega^{0}_{c}$ lifetime