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

24 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

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Cyclization
Alkylation
Hydrogenation
Glutarates
Carbonylation
Charcoal
Palladium
Benzene
Bromides
Derivatives
Oxidation
Catalysts
Acids
jasmonic acid
cyclopentenone
cyclopentanone
cyclopentanol
chromic acid
methyl acetoacetate

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Synthesis of methyl dl-jasmonate and its related compounds from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates. / Torii, Sigeru; Tanaka, Hideo; Kobayasi, Yuichi.

In: Journal of Organic Chemistry, Vol. 42, No. 22, 1977, p. 3473-3477.

Research output: Contribution to journalArticle

Torii, Sigeru ; Tanaka, Hideo ; Kobayasi, Yuichi. / Synthesis of methyl dl-jasmonate and its related compounds from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates. In: Journal of Organic Chemistry. 1977 ; Vol. 42, No. 22. pp. 3473-3477.
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title = "Synthesis of methyl dl-jasmonate and its related compounds from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates",
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.",
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T1 - Synthesis of methyl dl-jasmonate and its related compounds from methyl (E)- and (Z)-4,4-dimethoxy-2-butenoates

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N2 - 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.

AB - 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.

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