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Solid-phase Synthesis of [4.4] Spirocyclic Oximes
Published on: February 6, 2019
Stereoselective OsO4-catalyzed oxidative cyclization of 1,5-dienes
Alexander Poethig1, Thomas Strassner
1Technische Universität Dresden, 01062 Dresden, Germany.
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.
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