title: Catalytic, enantioselective, intramolecular carbosulfenylation of olefins. Preparative and stereochemical aspects.
abstract: The first catalytic, enantioselective, intramolecular carbosulfenylation of isolated alkenes with aromatic nucleophiles is described. The combination of N-phenylsulfenylphthalimide, a chiral selenophosphoramide derived from BINAM, and ethanesulfonic acid as a cocatalytic Brønsted acid induced an efficient and selective cyclofunctionalization of various alkenes (aliphatic and aromatic) tethered to a 3,4-methylenedioxyphenyl ring. Under these conditions, 6-phenylthio-5,6,7,8-tetrahydronaphthalenes are formed diastereospecifically in good yields (50-92%) and high enantioselectivities (71:29-97:3 er). E-Alkenes reacted much more rapidly and with much higher selectivity than Z-alkenes, whereas electron-rich alkenes reacted more rapidly but with comparable selectivity to electron-neutral alkenes and electron-deficient alkenes. The Brønsted acid played a critical role in effecting reproducible enantioselectivity. A model for the origin of enantioselectivity and the dependence of rate and selectivity on alkene structure is proposed along with a rationale for the site selectivity in reactions with monoactivated arene nucleophiles.
authors: Roger Adams Laboratory, Department of Chemistry, University of Illinois , Urbana, Illinois 61801, United States.
authors: Scott E
authors: SE
authors: Denmark
authors: Alex
authors: A
authors: Jaunet
mesh_terms: D000475:Alkenes / Q000737:chemistry*; D002384:Catalysis; D009281:Naphthalenes / Q000737:chemistry*; D010797:Phthalimides / Q000737:chemistry*; D013237:Stereoisomerism; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: C000590961:6-phenylthio-5,6,7,8-tetrahydronaphthalene; D000475:Alkenes; D009281:Naphthalenes; D010797:Phthalimides; D013438:Sulfhydryl Compounds