Filling some blanks in a divergent approach to gabosines

The levorotatory enantiomers of gabosines D and E were synthesized through a divergent approach that could equally well be applied to the synthesis of the dextrorotatory enantiomers, which have been isolated from natural sources. The approach relies on an initial desymmetrization of p-methoxyphenol,...

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Detalles Bibliográficos
Autores: Fresneda Quesada, Miguel Angel, Alibés, Ramon|||0000-0002-7997-2691, Bayón, Pau|||0000-0002-3064-8866, Figueredo Galimany, Marta|||0000-0002-8278-7534
Tipo de recurso: artículo
Fecha de publicación:2016
País:España
Institución:Universitat Autònoma de Barcelona
Repositorio:Dipòsit Digital de Documents de la UAB
Idioma:inglés
OAI Identifier:oai:ddd.uab.cat:279311
Acceso en línea:https://ddd.uab.cat/record/279311
https://dx.doi.org/urn:doi:10.1002/ejoc.201600492
Access Level:acceso abierto
Palabra clave:Cyclitols
Divergent synthesis
Eantioselectivity
Gabosines
Natural products
Descripción
Sumario:The levorotatory enantiomers of gabosines D and E were synthesized through a divergent approach that could equally well be applied to the synthesis of the dextrorotatory enantiomers, which have been isolated from natural sources. The approach relies on an initial desymmetrization of p-methoxyphenol, followed by an enzymatic resolution that separately provides the two enantiomers of synthon 3. This versatile synthon can be further transformed into the diverse polyoxygenated cyclohexane target molecules. Key steps in the synthesis of (-)-gabosines D and E from (4R,6S)-3 are the stereoselective hydroxymethylation at the α-carbonyl position leading to (+)-4, and the subsequent reagent-controlled epoxidation of the carbon-carbon double bond. A branching in the sequence also allowed the synthesis of the anhydrogabosines (-)-epiepoxydon and (+)-phyllostine.