SummaryAn unexpected reactivity of the superoxide ion leading to the synthesis of tetrachloroaryl/vinyl-substituted nortricyclenes through its dual mode of action has been reported. KO2 was found to be superior and the only reagent to perform this kind of reaction over other conventional bases. Addition of the antioxidant BHT (2,6-di-tert-butyl-4-methylphenol) improved the yields of methylenenortricyclenes. A complete deuterium incorporation was observed in the superoxide-mediated reaction in DMSO-d
6. Friedel–Crafts acylation reactions of 3-methylenenorticyclenes yielded 2-propanone-substituted pentachloronorbornenes.
The base-mediated formation of a bridgehead double bond in a bicyclo[2.2.1]heptane system (anit-Bredt molecules) is described. The synthesis of exocyclic norbornyl enones by Wittig reaction of α-diketones is reported. These enones and their Michael adducts are used as substrates for the generation of transient bridgehead enones and their trapping with MeOH and H2 O. Bridgehead alcohols are easily synthesized from norbornyl enones and are exploited for the diversity oriented synthesis of frameworks of natural and unnatural products.
Superoxide Mediated Isomerization of 4-Aryl-but-1-ynes to 1-Aryl-1,3-butadienes. -The title isomerizations of the substrates having disubstitution at benzylic position give different products depending on the nature of the substitution. The products can be further used for Diels-Alder reaction. -(KHAN*, F. A.; BUDANUR, B. M.; Tetrahedron 71 (2015) 40, 7600-7607, http://dx.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.