Synthesis of 2-acetyl-5-(1,2,3,4,5,6-hexahydroxyhexyl)thiazoles

Ung, Alison T.; Pyne, Stephen G.; Jeoffreys, George R.; Skelton, Brian W.; White, Allan H.

doi:10.1007/s00706-011-0448-z

Cited by 3 publications

(1 citation statement)

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“…Computational studies provide some insight into the origin of the stereoselectivity. Although α-silyloxy ketones can exhibit a range of conformers in the solid state, − calculations for ketone 20 in THF (B3LYP/6-31G* with the polarized continuum model to account for the influence of solvent) suggest that the conformer with the dipoles aligned, as illustrated by conformer 43 (Figure ), represents the lowest-energy family of conformers (by more than 1 kcal/mol). These conformers position the silyloxy group on one face of the carbonyl group and the alkyl group on the other face, differing only in the orientation of the groups on silicon.…”

Section: Resultsmentioning

confidence: 99%

Conformationally Biased Ketones React Diastereoselectively with Allylmagnesium Halides

et al. 2022

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The addition of the highly reactive reagent allylmagnesium halide to α-substituted acyclic chiral ketones proceeded with high stereoselectivity. The stereoselectivity cannot be analyzed by conventional stereochemical models because these reactions do not conform to the requirements of those models. Instead, the stereoselectivity arises from the approach of the nucleophile to the most accessible diastereofaces of the lowest-energy conformations of the ketones. High stereoselectivity is expected, and the stereochemical outcome can be predicted, with conformationally biased ketones that have sterically distinguishable diastereofaces wherein only one face is accessible for nucleophilic addition. The conformations of the ketones can be determined by a combination of computational modeling and, in some cases, structure determination by X-ray crystallography.

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Section: Resultsmentioning

confidence: 99%

Conformationally Biased Ketones React Diastereoselectively with Allylmagnesium Halides

et al. 2022

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ChemInform Abstract: Synthesis of 2‐Acetyl‐5‐(1,2,3,4,5,6‐hexahydroxyhexyl)thiazoles.

et al. 2011

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Synthesis of 2-Acetyl-5-(1,2,3,4,5,6-hexahydroxyhexyl)thiazoles. -The synthesis of two diastereomers of the title compound involves the coupling of 5-lithiated 2-(1,1-dimethoxyethyl)thiazole (VI) with a Weinreb amide (V) derived from gluconolacetone, followed by asymmetric reduction of the ketone functionality. -(UNG*, A. T.; PYNE, S. G.; JEOFFREYS, G. R.; SKELTON, B. W.; WHITE, A. H.; Monatsh. Chem. 142 (2011) 3, 297-303, http://dx.

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