Identification of a sulfide derivative with a bicyclic hydrocarbon skeleton related to squalene. Part I: synthesis of a dithiane triterpenoid

Abstract

In order to confirm the tentative structure of a dithiane sulfide with a bicyclic squalene hydrocarbon skeleton representing the predominant alkyl sulfide in Shell Beach samples from the Monterey Formation (Miocene, CA) and also occurring in various immature sulphur-rich sediments [Schouten, S., Sinninghe Damsté, J.S., de Leeuw, J.W., 1995. A novel triterpenoid carbon skeleton in immature sulphur-rich sediments. Geochimica et Cosmochimica Acta 59, 953–958], synthesis of a reference compound bearing two thiochromane moieties has been carried out. The product was obtained as a diastereomeric mixture appearing in the form of five peaks (partly) resolved in gas chromatography (GC). This is in sharp contrast with the geochemical compound, which appears as a single broad peak in GC. Co-elution experiments showed that none of the peaks from the synthetic mixture coelute in GC with that of the geochemical sulfide. Furthermore, the different synthetic isomers have identical mass spectra, which are clearly distinct from that of the naturally-occurring compound. The results unambiguously indicate that the natural compound is not the dithiane triterpenoid originally envisaged. Instead, we propose that the compound has a structure of a bicyclic squalene derivative bearing two “S-spiro”-type moieties as is the case for other sulfides related to regular polycyclic polyprenoids and hopanoids in Monterey sediments.