Total synthesis of acanthacerebroside A and astrocerebroside A via a chiral epoxide intermediate derived from L-quebrachitol

Noritaka Chida, Noboru Sakata, Katsuyuki Murai, Takahiko Tobe, Toshihiko Nagase, Seiichiro Ogawa

Research output: Contribution to journalArticle

23 Citations (Scopus)

Abstract

The chiral and stereoselective total synthesis of novel cerebrosides, acanthacerebroside A (1) and astrocerebroside A (2), isolated from starfish, is described. The phytosphingosine moieties in 1 and 2 were prepared by the coupling reaction of dialkylmagnesium reagents with the common epoxide intermediate, 2-(t-butoxycarbonyl)amino-1-O-(t-butyldiphenylsilyl)-2-deoxy- 3-O-(4-methoxybenzyl)-D-4,5-anhydroribitol (5). The epoxide (5) was synthesized from naturally occurring cyclitol, L-quebrachitol via the conduramine derivative, which was prepared regio- and stereoselectively by the Pd-catalyzed azidation of the allyl carbonate derivative. Condensation of phytosphingosines with 2-acetoxy fatty acid residue, followed by glycosidation, furnished the total synthesis. This work established an effective synthetic pathway to a wide variety of cerebrosides containing various phytosphingosines and 2-hydroxy fatty acid residue; the first total synthesis of astrocerebroside A (2) fully confirmed the proposed structure.

Original languageEnglish
Pages (from-to)259-272
Number of pages14
JournalBulletin of the Chemical Society of Japan
Volume71
Issue number1
DOIs
Publication statusPublished - 1998 Jan

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phytosphingosine
Epoxy Compounds
Cerebrosides
Cyclitols
Fatty Acids
Derivatives
Carbonates
Condensation
quebrachitol

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Total synthesis of acanthacerebroside A and astrocerebroside A via a chiral epoxide intermediate derived from L-quebrachitol. / Chida, Noritaka; Sakata, Noboru; Murai, Katsuyuki; Tobe, Takahiko; Nagase, Toshihiko; Ogawa, Seiichiro.

In: Bulletin of the Chemical Society of Japan, Vol. 71, No. 1, 01.1998, p. 259-272.

Research output: Contribution to journalArticle

Chida, Noritaka ; Sakata, Noboru ; Murai, Katsuyuki ; Tobe, Takahiko ; Nagase, Toshihiko ; Ogawa, Seiichiro. / Total synthesis of acanthacerebroside A and astrocerebroside A via a chiral epoxide intermediate derived from L-quebrachitol. In: Bulletin of the Chemical Society of Japan. 1998 ; Vol. 71, No. 1. pp. 259-272.
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