Synthesis of Stegobiol and Its Oxidation to Stegobinone, the Components of the Female-Produced Sex Pheromone of the Drugstore Beetle

Mori, Kenji; Сано, С.; Yokoyama, Yūsuke; Bando, Mai; Kido, Masaru

doi:10.1002/(sici)1099-0690(199806)1998:6<1135::aid-ejoc1135>3.0.co;2-k

Cited by 14 publications

(4 citation statements)

References 26 publications

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“…The most accessible (commercially and synthetically) of these ligands are the diphenylacetyl ligands ( R , R )- and ( S , S )- 40 , which can be used with either hafnium or zirconium, although the former generally affords higher yields and enantioselectivities . Ligands ( R,R )- 40 and ( S,S )- 40 were synthesized using the previously reported procedures, , and asymmetric epoxidation was then attempted (Scheme ). Although yields were lower than reported (45–60% after 72 h), the epoxidation did proceed with both ligands; no differences were observed between commercially available ( R , R )- 40 and ( R , R )- 40 synthesized in-house.…”

Section: Resultsmentioning

confidence: 60%

Asymmetric Total Synthesis of 19,20-Epoxydocosapentaenoic Acid, a Bioactive Metabolite of Docosahexaenoic Acid

Cinelli

Lee

2019

J. Org. Chem.

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In this study, we report the first asymmetric total synthesis of 19,20-epoxydocosapentaenoic acid (19,20-EDP), a naturally occurring bioactive cytochrome P450 metabolite of docosahexaenoic acid, a major constituent of fish oil. Our strategy involves direct asymmetric epoxidation to produce an enantiopure β-epoxyaldehyde that can be appended to the rest of the skipped polyene core by Wittig condensation. Our route is step-economical and late divergent and could be an appealing method by which to synthesize EDP analogues for biological studies.

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Section: Resultsmentioning

confidence: 60%

Asymmetric Total Synthesis of 19,20-Epoxydocosapentaenoic Acid, a Bioactive Metabolite of Docosahexaenoic Acid

Cinelli

Lee

2019

J. Org. Chem.

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“…The stereostructure of our crystalline stegobinone (5) was confirmed as 2S,3R,1ЈR by X-ray analysis. 20 The IR, NMR, and CD spectra of our synthetic 5 were identical to those of the natural product.…”

Section: Chirality and Insect Pheromonesmentioning

confidence: 64%

“…2. 20 Starting from diethyl ketone (7) and (E)-2-penten-1-ol (10), pure and crystalline 5 and 6 were prepared by employing our key cyclization reaction (14 → 15). 17,18 The racemic alcohol (±)-8 derived from 7 was subjected to asymmetric acetylation with vinyl acetate in the presence of Novozyme 435 (a lipase from Candida antarctica) to give the desired (4R,8S)-8 as the recovered and non-acetylated aldol.…”

Section: Synthesis Of Stegobinone the Drugstore Beetle Pheromonementioning

confidence: 99%

Chirality and insect pheromones

Mori

1998

Chirality

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Enantioselective synthesis is a central component of research on the effect of chirality on the relationships between pheromone structure and pheromone bioactivity. The syntheses of stegobinone, the drugstore beetle pheromone, and frontalin, a bark beetle pheromone, are reported as examples of stereocontrolled synthesis. Chirality governs the biodiversity of pheromone perception, as illustrated by the discussion on the relationships between absolute configuration and pheromone activity. Chirality 10:578–586, 1998. © 1998 Wiley‐Liss, Inc.

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“…Acylation of (4R,5S)-8 with 13 afforded 14. 20 The IR, NMR, and CD spectra of our synthetic 5 were identical to those of the natural product. We therefore used Oppolzer's method 21 to cyclize 14 to 15 by treatment with titanium(IV) tetrachloride and diisopropylethylamine.…”

Section: Chirality and Insect Pheromonesmentioning

confidence: 67%