Stereoselective epoxidation of divinylmethanol: A synthetic approach to the pentitols

David Holland*, J. Fraser Stoddart

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Scopus citations

Abstract

Peroxy-acid epoxidation of divinylmethanol (9), followed by acetylation afforded the acetylated monoepoxides 1 and 2 having the erythro (53%) and threo (47%) configurations. Peroxy-acid epoxidation of 1 and 2 yielded the acetylated diepoxides 3 (erythro-erythro, 36%) and 4 (erythro-threo, 64%) (from 1), and 4 (erythro-threo, 47%) and 5 (threo-threo, 53%) (from 2). Relative configurational assignments were made to 1-5 on the basis of (a) 1H-n.m.r. chemical-shift and coupling-constant data, (b) the observation that 1 gave only 3 and 4, and that 2 gave only 4 and 5 on epoxidation, and (c) the fact that 3-5 separately undergo epoxide-ring opening preferentially at their primary carbon atoms with acetate ion in acetic anhydride, to afford the penta-acetates of ribitol, dl-arabinitol, and xylitol, respectively, as major products. Epoxide-ring formation favours the erythro configuration when either peroxy acids or tert-butyl hydroperoxide with catalytically active Ti4+, V5+, or Mo6+ complexes are employed as epoxidation reagents. However, the diastereoselectivities characterising the epoxidations and the regioselectivities governing the epoxide-ring openings are not sufficiently high to constitute an attractive synthesis of either ribitol, dl-arabinitol, or xylitol from divinylmethanol. {A figure is presented}.

Original languageEnglish (US)
Pages (from-to)207-220
Number of pages14
JournalCarbohydrate Research
Volume100
Issue number1
DOIs
StatePublished - 1982

ASJC Scopus subject areas

  • Analytical Chemistry
  • Biochemistry
  • Organic Chemistry

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