RESUMEN
A general and stereospecific homologation strategy for the synthesis of heptopyranosides is reported. The strategy employs the Wittig olefination and proline-catalyzed α-aminoxylation to achieve one carbon elongation and stereoselective hydroxylation at the C6 position, respectively. The L-glycero- and D-glycero-heptopyranosides can be obtained with nearly perfect stereoselectivity. Further study reveals the difference in the chemical shift of the C6 proton of L/D-glycero-heptopyranosyl diastereomers, which is found to be useful for assignment of the configuration of heptopyranosides.
Asunto(s)
Heptosas/síntesis química , Glicósidos/síntesis química , Glicósidos/química , Heptosas/química , Estructura Molecular , Estereoisomerismo , Relación Estructura-ActividadRESUMEN
A general strategy for the synthesis of phenylethanoid glycosides (PhG) including echinacoside 1, acteoside 2, calceolarioside-A 3 and calceolarioside-B 4 is reported. The strategy features the application of low substrate concentration glycosylation and N-formyl morpholine modulated glycosylation methods for the construction of 1,2-trans ß- and α-glycosidic bonds. The reported strategy does not invoke the use of the participatory acyl protecting function, which is incompatible with the ester function present in target PhG compounds. A preliminary study of the anti-proliferation properties of the PhG compounds 14 was performed; the acteoside 2 exhibited the best inhibition on the prostatic cancer cell proliferation.
Asunto(s)
Química Orgánica/métodos , Glicósidos/farmacología , Alcohol Feniletílico/farmacología , Neoplasias de la Próstata/patología , Ácidos Cafeicos/síntesis química , Ácidos Cafeicos/química , Ácidos Cafeicos/farmacología , Línea Celular Tumoral , Proliferación Celular/efectos de los fármacos , Glucósidos/síntesis química , Glucósidos/química , Glucósidos/farmacología , Glicósidos/síntesis química , Glicósidos/química , Humanos , Masculino , Fenoles/síntesis química , Fenoles/química , Fenoles/farmacología , Alcohol Feniletílico/químicaRESUMEN
The major challenge in carbohydrate synthesis is stereochemical control of glycosidic bond formation. Different glycosylation methods have been developed that are based on the modulation effect of external nucleophiles. This review highlights the development, synthetic application, challenges and outlook of the modulated glycosylation methods.