Intrazeolite photooxygenation of chiral alkenes. Control of facial selectivity by confinement and cation-π interactions

Depending on the nature of the substituents on the stereogenic carbon atom, the ene reaction of singlet oxygen with several chiral alkenes by confinement within thionin-supported zeolite NaY, may exhibit significant changes on facial selectivity by comparison to their photooxygenation reaction in solution. It is proposed that, apart from the conformational consequences as a result of the alkene confinement within the zeolite cavities, a synergism between Na⁺-π interactions and singlet oxygen-Na⁺ interactions plays a significant role in the transition states of ene hydroperoxidation. Within NaY, the diastereoselectivity may significantly depend on the site selectivity, as probed through specific deuterium labelling of trisubstituted alkenes bearing a gem-dimethyl group. In certain cases, a remote stereogenic centre relative to the reacting double bond may induce enhanced diastereoselection and regioselectivity.     

Gravitational Influence on Human Living Systems and the Evolution of Species on Earth

Gravity constituted the only constant environmental parameter, during the evolutionary period of living matter on Earth. However, whether gravity has affected the evolution of species, and its impact is still ongoing. The topic has not been investigated in depth, as this would require frequent and long-term experimentations in space or an environment of altered gravity. In addition, each organism should be studied throughout numerous generations to determine the profound biological changes in evolution. Here, we review the significant abnormalities presented in the cardiovascular, immune, vestibular and musculoskeletal systems, due to altered gravity conditions. We also review the impact that gravity played in the anatomy of snakes and amphibians, during their evolution. Overall, it appears that gravity does not only curve the space–time continuum but the biological continuum, as well.     

Functionalized 3(2H)-furanones via photooxygenation of (β-keto)-2-substituted furans: application to the biomimetic synthesis of merrekentrone C

Photooxygenation of (β-keto)-2-substituted furans leads, in a one pot operation, to functionalized 3(2H)-furanones with good to excellent yields. This methodology was applied as a key-step to the concise and biomimetic synthesis of the sesquiterpene merrekentrone C. The precursor to merrekentrone C, keto difuran, was synthesized using a cross coupling of α-iodo-3-acetylfuran with an alkenyl furan under Fenton-type conditions.