Synthesis of methyl dl-jasmonate and its related compounds from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates

Sigeru Torii, Hideo Tanaka, Yuichi Kobayasi

Research output: Contribution to journalArticle

25 Citations (Scopus)

Abstract

A synthesis of methyl dl-jasmonate (1b) and its dehydro derivatives 2b and 3b from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates (4) is described. Dimethyl 2-acetyl-3-dimethoxymethylglutarate (5) could be obtained by Michael addition of 4 with methyl acetoacetate in excellent yields. Deacetalization of dimethyl 2-acetyl-3-di-methoxymethyl-2-(2-pentynyl)glutarate (7a) followed by cyclization with base after alkylation of 5 (R′ = Me) with 2-pentynyl bromide afforded 5-methoxycarbonyl-4-methoxycarbonylmethyl-5-(2-pentynyl)-2-cyclopentenone (10a). Reduction of 10 (R′ = Me) with NaBH4 in MeOH giving 2-methoxycarbonyl-3-methoxycarbonylmethyl-2-(2-pentynyl)cyclopentanol (13a) and subsequent oxidation of 13 with chromic acid gave 2-methoxycarbonyl-3-methoxycarbonylmethyl-2-(2-pentynyl)cyclopentanone (14a), a precursor of 1b. Cis hydrogenation of 7a → 7b, 10a → 10b, 13a → 13b, and 14a → 14b using Lindlar catalyst proceeded in quantitative yields. Direct demethoxy-carbonylation of 10b (R = 2-cis-pentenyl) with Me2SO-H2O-NaCl in a sealed tube afforded a mixture of 2b and 3b. However, acid-catalyzed de-tert-butoxycarbonylation of 10b (R′ = t-Bu), prepared from 5 (R′ = t-Bu) by alkylation followed with cyclization, under reflux in benzene gave 2b as a sole product. Hydrogenation of 10a with palladium on charcoal afforded 14c (R = pentyl). The products 2b and 3b could be converted into 1b smoothly.

Original languageEnglish
Pages (from-to)3473-3477
Number of pages5
JournalJournal of Organic Chemistry
Volume42
Issue number22
Publication statusPublished - 1977

ASJC Scopus subject areas

  • Organic Chemistry

Fingerprint Dive into the research topics of 'Synthesis of methyl dl-jasmonate and its related compounds from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates'. Together they form a unique fingerprint.

  • Cite this