Stereoselective OsO4-catalyzed oxidative cyclization of 1,5-dienes.
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.
Poethig
Alexander
A
Technische Universität Dresden, 01062 Dresden, Germany.
Strassner
Thomas
T
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
D009993:Osmium Tetroxide