Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part II: synthesis of a S-spiro-like dithiolane triterpenoid

A sulfide with a bicyclic squalene hydrocarbon skeleton present in sediments from various depositional settings and of different geological age has been identified by synthesis of a reference compound. In contrast to previous expectations [cf. Schouten, S., Sinninghe Damste, J.S., de Leeuw, J.W., 1995. A novel triterpenoid carbon skeleton in immature sulphur-rich sediments. Geochimica et Cosmochimica Acta 59, 953–958; Gug, S., Schaeffer, P., Adam, P., Klein, S., Motsch, E., Albrecht, P., 2009. Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: Synthesis of a dithiane triterpenoid. Organic Geochemistry 40, 876–884.], this sulfide bears two “S-spiro type“ thiolane moities, but not the two thiochromane moieties originally envisaged. The synthesis resulted in the formation of a complex isomeric mixture of compounds, all co-eluting in gas chromatography (GC) in the form of one broad peak, as is the case with the geochemical compound. The spiro-type sulfide was formed by intramolecular sulfurization of a polyunsaturated bicyclic squalene derivative of unknown biological origin. The presence of this sulfide in a number of Triassic to Miocene marine sediments from various and contrasting depositional settings (upwelling environments, shallow continental platforms, lagoonal sub-basins, hypersaline environments), all characterized by strongly anoxic conditions, but with or without photic zone anoxia, indicates that the microorganisms biosynthesizing the precursor bicyclic squalene occupy diverse ecological niches.