Vanadium-catalyzed selenide oxidation with in situ[2,3] sigmatropic rearrangement (SOS reaction): scope and asymmetric applications.
A vanadium-catalyzed method for the oxidation of prochiral aryl, allylic selenides with tandem [2,3] sigmatropic rearrangement has been developed. This protocol has been screened on a series of substrates to test for its generality and effectiveness. The applicability of this methodology to the synthesis of enantiomerically enriched allylic alcohols has been studied on a series of chiral oxazole-containing systems with a diastereomeric ratio (d.r.) of up to 85 : 15. The chiral transfer observed in the allyl alcohol products is the result of a net 1,9- and/or 1,10-induction. Finally, the first example of a selenium-oxygen nonbonding interaction in oxazole-containing selenide appears to have been observed via X-ray crystal analysis.
Bourland
T Campbell
TC
Department of Chemistry, Oregon State University, Corvallis, OR 97331, USA.
Carter
Rich G
RG
Yokochi
Alexandre F T
AF
D002384:Catalysis; D018360:Crystallography, X-Ray; D008958:Models, Molecular; D008968:Molecular Conformation; D016566:Organoselenium Compounds / Q000138:chemical synthesis / Q000737:chemistry; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D014639:Vanadium / Q000737:chemistry*
D016566:Organoselenium Compounds; D014639:Vanadium