“…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.…”
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.
“…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.…”
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.
“…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
“…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
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.
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