The carbohydrate-sesquiterpene interface. A zirconocene-mediated synthesis of (+)-epiafricanol from D-glucose

A total synthesis of (+)-epiafricanol (6) has been readily achieved from D-glucose. The tricyclic alcohol target was arrived at by first forming m, ethyl 6-O-benzyl-2-deoxy-2-C-methyl-alpha-D-altropyranoside (12) and converting this intermediate into methyl 2-C-methyl-2,3,4-trideoxy-alpha-D-threo-he...

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Bibliographic Details
Published inSynthesis (Stuttgart) no. 14; pp. 2105 - 2109
Main Authors Paquette, LA, Arbit, RM, Funel, JA, Bolshakov, S
Format Journal Article
LanguageEnglish
Published STUTTGART Thieme Medical Publishers 01.01.2002
Subjects
Chemistry
Chemistry, Organic
Physical Sciences
Science & Technology
ORGANIC-SYNTHESIS
(+/-)-AFRICANOL
glucose
ACETALS
sesquiterpene
ALKENES
DIENES
zirconocene
metathesis
REDUCTION
(+/-)-ISOAFRICANOL
CONSTRUCTION
ring contraction
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Summary:A total synthesis of (+)-epiafricanol (6) has been readily achieved from D-glucose. The tricyclic alcohol target was arrived at by first forming m, ethyl 6-O-benzyl-2-deoxy-2-C-methyl-alpha-D-altropyranoside (12) and converting this intermediate into methyl 2-C-methyl-2,3,4-trideoxy-alpha-D-threo-hexopyranoside (14). There followed a series of steps resulting in extension of the side chain to give the isopropenyl pyranoside 9. This advanced intermediate was subjected to zirconocene-promoted ring contraction, which gave rise to 8 and set the stage for conversion to 7. This tertiary carbinol was transformed into 6 by sequential ring-closing metathesis and stereodirected Simmons-Smith cyclopropanation.
ISSN:0039-7881
DOI:10.1055/s-2002-34380