RESUMO
Difluorinated cyclooctenones, synthesised using RCM, can be used as templates for stereoselective oxidative transformations to products that undergo transannular reactions to afford conformationally-locked analogues of 2-deoxy-2,2-difluorosugars with different stereochemical relationships between the C-2 and C-3 hydroxyl groups.
Assuntos
Desoxiaçúcares/química , Flúor/química , Configuração de Carboidratos , Ciclização , Hidroxilação , EstereoisomerismoRESUMO
[reaction: see text] A new route, of potential strategic importance, to a difluorosugar analogue has been developed. Key steps included a Stille coupling and a highly regio- and enantioselective dihydroxylation of a highly substituted diene. Protecting groups were chosen to enhance the reactivity of the disubstituted allylic fragment in the AD reaction and allow deprotection under orthogonal conditions.
Assuntos
Xilulose/análogos & derivados , Xilulose/síntese química , Espectroscopia de Ressonância Magnética , Estrutura Molecular , Estereoisomerismo , Xilulose/químicaRESUMO
Metallated haloalkenes were used to open epoxides in moderate to good yield. The homoallylic alcohols obtained underwent Swern oxidation to afford three gamma,gamma-difluorinated beta,gamma-enones, which reacted with either vinyllithium,2-lithio-2H-dihydropyran or another metallated haloalkene to afford substituted trans-1,2-divinylcyclohexanols of different degrees of stability. These intermediates underwent neutral thermal oxy-Cope rearrangements when heated in xylene in Ace tubes. The first-formed enols ketonised without loss of HF to afford a range of cyclodecenones in moderate to good yield; X-ray crystallography was used extensively for product characterisation. All substrates rearranged more rapidly than a cis/trans mixture of 1,2-divinylcyclohexanols.
Assuntos
Flúor/química , Compostos Heterocíclicos/síntese química , Hidrocarbonetos Fluorados/síntese química , Cristalografia por Raios X , Compostos de Epóxi/síntese química , Compostos de Epóxi/química , Compostos Heterocíclicos/química , Hidrocarbonetos Fluorados/química , Espectroscopia de Ressonância Magnética , Modelos Químicos , Modelos Moleculares , Conformação Molecular , EstereoisomerismoRESUMO
Diels-Alder and conjugate addition reactions were used to prepare precursors to a range of fully functionalized and deoxy inositol phosphate analogues.
Assuntos
Fosfatos de Inositol/síntese química , Cicloexanos/química , Mimetismo Molecular , EstereoisomerismoRESUMO
Building block methodology from trifluoroethanol and ring-closing metathesis using a Fürstner modification of Grubbs' conditions allows the rapid synthesis of novel difluorinated cyclooctenones.