First Total Synthesis of Acerogenin C and Aceroside IV

Strategically positioned arom. rings could switch the polyhydrocarbon chain from its normal extended conformation into folded one by the principle of intramol. recognition phenomena, favoring thus the intramol. reaction if these two arom. rings are correctly functionalized. Based on this conception, a new strategy for the synthesis of macrocyclic diarylheptanoids has been developed and convergent total syntheses of acerogenin C (I) (R = H) (II) and aceroside IV (I) (R = beta -D-glucopyranosyl) (III) were accomplished. Cycloetherification of linear diarylheptanoid: 1-(4-fluoro-3-nitrophenyl)-7-(3-hydroxy-4-methoxyphenyl)-heptan-3-one under mild conditions (CsF, DMF, rt) gave the macrocycle: 4-methoxy-17-nitro-2-oxa-tricyclo (13,2,23,7) eicosa-1(18),3,5,7(20),15(19),16-hexaen-12-one in 95% yield. Removal of nitro group followed by O-demethylation gave II. Glucosidation of II followed by sapon. give III in excellent overall yield. [on SciFinder (R)]

Published in:
Journal of Organic Chemistry, 62, 22, 7544-7545
CAN 127:307245
Biomolecules and Their Synthetic Analogs
Institut de Chimie des Substances Naturelles,CNRS,Gif-sur-Yvette,Fr.
written in English.
105-45-3 (Methyl acetoacetate); 60432-34-0; 114682-36-9; 129150-61-4; 197382-96-0; 197382-99-3 Role: RCT (Reactant), RACT (Reactant or reagent) (total synthesis of acerogenin C and aceroside IV); 57627-75-5P; 197382-79-9P; 197382-88-0P; 197382-90-4P; 197382-92-6P; 197382-94-8P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (total synthesis of acerogenin C and aceroside IV); 74390-30-0P (Aceroside IV); 87425-32-9P (Acerogenin C) Role: SPN (Synthetic preparation), PREP (Preparation) (total synthesis of acerogenin C and aceroside IV)

 Record created 2010-11-25, last modified 2018-03-17

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