Lead tetraacetate mediated domino reactions on ( R)-(−)-carvone-derived bicyclic unsaturated 1,2-diols and further rearrangements

Carvone derived octaline diols 1 and 2 were subjected to Pb(OAc) 4-mediated glycol fission conditions. The isolable ‘half-cascade’ intermediate 3 was subjected to ozonolysis in methylene chloride, and subsequent basic treatment, providing bis-angularly substituted bicyclic lactone 5 via an intramole...

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Bibliographic Details
Published in:Tetrahedron: asymmetry 2003-08, Vol.14 (15), p.2277-2290
Main Authors: Sanchez Fernandez, Elena M., Candela Lena, José I., Altinel, Ertan, Birlirakis, Nicolas, Barrero, Alejandro F., Arseniyadis, Siméon
Format: Article
Language:English
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Summary:Carvone derived octaline diols 1 and 2 were subjected to Pb(OAc) 4-mediated glycol fission conditions. The isolable ‘half-cascade’ intermediate 3 was subjected to ozonolysis in methylene chloride, and subsequent basic treatment, providing bis-angularly substituted bicyclic lactone 5 via an intramolecular Cannizzaro type oxidoreduction. The ring expanded products 4 and 6 subjected to basic treatment afforded bicyclic aldols 8 and 7, respectively, via a fused-to-bridged ring system interchange. The methods described here represent efficient approaches to a variety of conveniently functionalized chiral backbones offering chemoselectivity. The mechanistic pathways involved in both the oxidative cleavage induced domino transformations and in the base-induced ring-system interchange reactions are discussed. The synthesis and oxidative cleavage reactions of carvone derived 1,2-unsaturated diols 1 and 2 are described.
ISSN:0957-4166
1362-511X
DOI:10.1016/S0957-4166(03)00480-4