RESUMO
A stereodivergent total synthesis has been executed based on the plausibly misassigned structure of the unusual marine hydrindane mucosin (1). The topological connectivity of the four contiguous all-carbon stereocenters has been examined by selective permutation on the highlighted core. Thus, capitalizing on an unprecedented stereofacial preference of the cis-fused bicycle[4.3.0]non-3-ene system when a Michael acceptor motif is incorporated, copper-mediated conjugate addition furnished a single diastereomer. Cued by the relative relationship reported for the appendices in the natural product, the resulting anti-adduct was elaborated into a probative target structure 1*.
Assuntos
Produtos Biológicos/química , Compostos Bicíclicos Heterocíclicos com Pontes/química , Indanos/química , Estrutura Molecular , EstereoisomerismoRESUMO
Three different protocols for the syntheses of hydroxyalkylnitramines are presented and compared. Safety issues regarding the synthesis of nitramines are also discussed.
Assuntos
Compostos de Anilina/síntese química , Técnicas de Química Sintética , Nitrobenzenos/síntese química , Carbamatos/química , Dióxido de Carbono/química , Cromatografia Líquida de Alta Pressão , Espectroscopia de Ressonância Magnética , Ácido Nítrico/química , Espectrometria de Massas por Ionização por Electrospray , Espectroscopia de Infravermelho com Transformada de FourierRESUMO
The first total synthesis aimed at the naturally occurring eicosanoid bicycle mucosin is reported. A practical route has been devised allowing the issues relating to the previous assignment of stereochemistry to be examined. X-ray crystallography was performed on a late stage intermediate to pinpoint the topological relationship displayed by the featured bicyclo[4.3.0]non-3-ene scaffold.
