Electrolytic decarboxylation reactions. II. Syntheses of methyl dihydrojasmonate and methyl dl-jasmonate from 3-methoxycarbonyl-2-carboxynorbornane via anodic acetoxylation

Sigeru Torii, Hideo Tanaka, Tadakatsu Mandai

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

Methyl dihydrojasmonate (1a) and methyl dl-jasmonate (1b) were prepared from 3-methoxycarbonyl-2-carboxynorbornane (2a) via anodic acetoxylation. Electrolysis of 2a in a mixed solvent of AcOH-t-BuOH-Et3N gave a desired key intermediate, exo-2-acetoxy-anti-7-methoxycarbonylnorbornane (3), in 56% yield (GLC peak area) together with several minor products, 4 (12%), 5 (7%), 6 (11%), and 7 (4%). Hydrolysis of 3 followed by oxidation with chromic acid afforded 7-methoxycarbonyl-2-norbornanone (9) in good yield. The Baeyer-Villiger oxidation of 9 and subsequent hydrolysis and oxidation gave 2-methoxycarbonyl-3-methoxycarbonylmethylcyclopentanone (12) in 54% yield. Alkylation of 12 with pentyl and 2-pentynyl bromide and following cis hydrogenation and demethoxycarbonylation afforded 1a and 1b, efficiently.

Original languageEnglish
Pages (from-to)2221-2224
Number of pages4
JournalJournal of Organic Chemistry
Volume40
Issue number15
Publication statusPublished - 1975

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Oxidation
Hydrolysis
Alkylation
Bromides
Electrolysis
Hydrogenation
Decarboxylation
jasmonic acid
chromic acid
norcamphor

ASJC Scopus subject areas

  • Organic Chemistry

Cite this

Electrolytic decarboxylation reactions. II. Syntheses of methyl dihydrojasmonate and methyl dl-jasmonate from 3-methoxycarbonyl-2-carboxynorbornane via anodic acetoxylation. / Torii, Sigeru; Tanaka, Hideo; Mandai, Tadakatsu.

In: Journal of Organic Chemistry, Vol. 40, No. 15, 1975, p. 2221-2224.

Research output: Contribution to journalArticle

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abstract = "Methyl dihydrojasmonate (1a) and methyl dl-jasmonate (1b) were prepared from 3-methoxycarbonyl-2-carboxynorbornane (2a) via anodic acetoxylation. Electrolysis of 2a in a mixed solvent of AcOH-t-BuOH-Et3N gave a desired key intermediate, exo-2-acetoxy-anti-7-methoxycarbonylnorbornane (3), in 56{\%} yield (GLC peak area) together with several minor products, 4 (12{\%}), 5 (7{\%}), 6 (11{\%}), and 7 (4{\%}). Hydrolysis of 3 followed by oxidation with chromic acid afforded 7-methoxycarbonyl-2-norbornanone (9) in good yield. The Baeyer-Villiger oxidation of 9 and subsequent hydrolysis and oxidation gave 2-methoxycarbonyl-3-methoxycarbonylmethylcyclopentanone (12) in 54{\%} yield. Alkylation of 12 with pentyl and 2-pentynyl bromide and following cis hydrogenation and demethoxycarbonylation afforded 1a and 1b, efficiently.",
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N2 - Methyl dihydrojasmonate (1a) and methyl dl-jasmonate (1b) were prepared from 3-methoxycarbonyl-2-carboxynorbornane (2a) via anodic acetoxylation. Electrolysis of 2a in a mixed solvent of AcOH-t-BuOH-Et3N gave a desired key intermediate, exo-2-acetoxy-anti-7-methoxycarbonylnorbornane (3), in 56% yield (GLC peak area) together with several minor products, 4 (12%), 5 (7%), 6 (11%), and 7 (4%). Hydrolysis of 3 followed by oxidation with chromic acid afforded 7-methoxycarbonyl-2-norbornanone (9) in good yield. The Baeyer-Villiger oxidation of 9 and subsequent hydrolysis and oxidation gave 2-methoxycarbonyl-3-methoxycarbonylmethylcyclopentanone (12) in 54% yield. Alkylation of 12 with pentyl and 2-pentynyl bromide and following cis hydrogenation and demethoxycarbonylation afforded 1a and 1b, efficiently.

AB - Methyl dihydrojasmonate (1a) and methyl dl-jasmonate (1b) were prepared from 3-methoxycarbonyl-2-carboxynorbornane (2a) via anodic acetoxylation. Electrolysis of 2a in a mixed solvent of AcOH-t-BuOH-Et3N gave a desired key intermediate, exo-2-acetoxy-anti-7-methoxycarbonylnorbornane (3), in 56% yield (GLC peak area) together with several minor products, 4 (12%), 5 (7%), 6 (11%), and 7 (4%). Hydrolysis of 3 followed by oxidation with chromic acid afforded 7-methoxycarbonyl-2-norbornanone (9) in good yield. The Baeyer-Villiger oxidation of 9 and subsequent hydrolysis and oxidation gave 2-methoxycarbonyl-3-methoxycarbonylmethylcyclopentanone (12) in 54% yield. Alkylation of 12 with pentyl and 2-pentynyl bromide and following cis hydrogenation and demethoxycarbonylation afforded 1a and 1b, efficiently.

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