ABSTRACT
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*.
Subject(s)
Biological Products/chemistry , Bridged Bicyclo Compounds, Heterocyclic/chemistry , Indans/chemistry , Molecular Structure , StereoisomerismABSTRACT
Three different protocols for the syntheses of hydroxyalkylnitramines are presented and compared. Safety issues regarding the synthesis of nitramines are also discussed.
Subject(s)
Aniline Compounds/chemical synthesis , Chemistry Techniques, Synthetic , Nitrobenzenes/chemical synthesis , Carbamates/chemistry , Carbon Dioxide/chemistry , Chromatography, High Pressure Liquid , Magnetic Resonance Spectroscopy , Nitric Acid/chemistry , Spectrometry, Mass, Electrospray Ionization , Spectroscopy, Fourier Transform InfraredABSTRACT
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.
