title: Phosphorothioic acids and related compounds as surrogates for H2S--synthesis of chiral tetrahydrothiophenes.
abstract: The convenient preparation of chiral tetrahydrothiophenes (THTs) in high enantiopurity via phosphorothioic acids and related compounds is reported. We consider these to be safer alternatives to the use of H(2)S which is a highly toxic gas. Each of the THTs is derived from a common intermediate, thereby greatly enhancing the flexibility of the synthesis. The key transformation is a base-promoted, intramolecular, carbon-sulfur bond-forming event. These reactions are highly stereospecific as they operate through a double S(N)2 displacement mechanism. The methodology is amenable to a broad array of functional groups and heterocycles. The tetrahydrothiophene motif is important because it is present in a number of bioactive natural products. They have also been utilized to promote various asymmetric transformations including hydrogenation, epoxidation, cyclopropanation, and aziridination reactions.
authors.affiliation: Department of Chemistry, Dartmouth College, Hanover, New Hampshire 03755, USA.
authors.forename: Forest J
authors.initials: FJ
authors.lastname: Robertson
authors.forename: Jimmy
authors.initials: J
authors.lastname: Wu
mesh_terms: D018360:Crystallography, X-Ray; D006862:Hydrogen Sulfide / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D010710:Phosphates / Q000737:chemistry*; D013237:Stereoisomerism; D013876:Thiophenes / Q000138:chemical synthesis* / Q000737:chemistry
chemical_list: D010710:Phosphates; D013876:Thiophenes; C121030:tetrahydrothiophene; C035638:thiophosphoric acid; D006862:Hydrogen Sulfide