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DOI: 10.1055/s-2001-18717
2-Acetonyl-2,4-di(hydroxy)tetrahydropyrans versus γ-Pyrones: A Chemodivergent Issue for the Condensation of Acetylacetone Dianion Equivalents with α,β-Disubstituted β-Hydroxyaldehydes Leading to Potential New Synthons for Spiroketals
Publication History
Publication Date:
05 August 2004 (online)
Abstract
In order to develop a new route to ketal or spiroketal subunits present in numerous natural products, condensation of acetylacetone bis(silyl)enol ether 2-Si or acetylacetone lithium dianion 2-Li with various anti α,β-disubstituted β-hydroxy aldehydes 11 was studied. It has been shown that under Lewis acid-promoted Mukaiyama conditions it is possible to realize such condensation reactions without formation of the well-known Danishefsky γ-pyrones 8. The required 2-acetonyl-2,4-dihydroxytetrahydropyrans 1 for further synthetic purposes were prepared in good to high yields from the intermediate acyclic aldol adduct 7. Particularly crucial are i) the deprotection conditions of the O-silyl protected acyclic intermediate 7 with tetrabutylammonium fluoride in dimethylformamide, and ii) the subsequent montmorillonite K10-promoted protection of the hemiketal 1 hydroxy group. The parameters governing the stereoselectivity of the initial condensation reaction have been studied. Under apparent Felkin or anti-Felkin/Cram-chelate conditions, syn,anti-adducts are obtained with high selectivity from acetylacetone bis(silyl) enol ether 2-Si. Partial modulation of the stereoselectivity can be achieved through condensation of the acetylacetone lithium dianion 2-Li with aldehydes bearing bulky O-silyl protecting groups which allows a preferential access to the anti,anti triads.
Key words
silyl enols ethers - dianions - aldol reactions - cyclizations - chemoselectivity - diastereoselectivity - spiro compounds
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References
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2Current address: Jean-Pierre Férézou, Far-Manguinhos, Instituto Oswaldo Cruz, Rua Sizenando Nabuco, 100 Manguinhos, CEP 21041-250 Rio de Janeiro/RJ, Brazil, E-Mail: ferezou@gbl.com.br.
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