title: Stereoselective OsO4-catalyzed oxidative cyclization of 1,5-dienes.
abstract: The mechanism of the oxidation of 1,5-dienes with osmium tetroxide was investigated by density functional theory calculations (B3LYP/6-311+G*). The observed products, 2,5-bis(hydroxymethyl)tetrahydrofurans, are formed stereoselectively in a concerted reaction. Enantioselectivity could be induced by an enantioselective dihydroxylation followed by condensation of the 5,6-dihydroxyolefine with osmium tetroxide, while the diastereoselectivity is achieved by reaction of the 1,5-diene with osmium tetroxide and intermediate reoxidation of the osmium(VI) ester.
authors.affiliation: Technische Universität Dresden, 01062 Dresden, Germany.
authors.forename: Alexander
authors.initials: A
authors.lastname: Poethig
authors.forename: Thomas
authors.initials: T
authors.lastname: Strassner
mesh_terms: D002384:Catalysis; D003198:Computer Simulation; D003500:Cyclization; D015394:Molecular Structure; D009993:Osmium Tetroxide / Q000737:chemistry*; D010084:Oxidation-Reduction; D011789:Quantum Theory; D013237:Stereoisomerism; D013816:Thermodynamics
chemical_list: D009993:Osmium Tetroxide