2-acetonyl-2,4-di(hydroxy)tetrahydropyrans versus ?-pyrones: A chemodivergent issue for the condensation of acetylacetone dianion equivalents with a,ß-disubstituted ß-hydroxyaldehydes leading to potential new synthons for spiroketals - École polytechnique Access content directly
Journal Articles Synthesis: Journal of Synthetic Organic Chemistry Year : 2001

2-acetonyl-2,4-di(hydroxy)tetrahydropyrans versus ?-pyrones: A chemodivergent issue for the condensation of acetylacetone dianion equivalents with a,ß-disubstituted ß-hydroxyaldehydes leading to potential new synthons for spiroketals

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 a,ß-disubstituted ß-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 ?-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.
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hal-00954866 , version 1 (13-03-2014)

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Vivien Henryon, Roman Lopez, Joëlle Prunet, Jean-Pierre Férézou. 2-acetonyl-2,4-di(hydroxy)tetrahydropyrans versus ?-pyrones: A chemodivergent issue for the condensation of acetylacetone dianion equivalents with a,ß-disubstituted ß-hydroxyaldehydes leading to potential new synthons for spiroketals. Synthesis: Journal of Synthetic Organic Chemistry, 2001, 16, pp.2401-2414. ⟨10.1055/s-2001-18717⟩. ⟨hal-00954866⟩
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