Studies toward the Synthesis of Vinigrol. First Construction of the Tricyclic Ring System

Devaux, Jean-François; Hanna, Issam; Lallemand, Jean‐Yves

doi:10.1021/jo970343o

Cited by 39 publications

(3 citation statements)

References 22 publications

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“…The bicyclic scaffolds of 7 − 9 were envisioned to arise from two Diels−Alder reactions between dienes 12 and 23 , respectively, and a reactive electron-deficient ethene equivalent. Commercially available phenyl vinyl sulfone was the dienophile of choice since the electron-withdrawing sulfonyl group could be smoothly eliminated from the cycloaddition products . While the cycloaddition of diene 12 was expected to proceed uneventfully, the diastereoselectivity of the Diels−Alder reaction of diene 23 was rather unpredictable, though the bulky lateral substituent could, in principle, influence reagent approach.…”

Section: Resultsmentioning

confidence: 99%

“…It must be stressed that the success of the alkylation of sulfone 24 strongly depended on the use of DMPU as cosolvent, since in THF alone the reaction afforded significantly lower yields. With diene 23 in hands, our attention was directed to the study of the crucial Diels−Alder reaction with phenyl vinyl sulfone (Scheme ) . In the event, the cycloaddition of 23 proceeded satisfactorily at a temperature significantly higher than that for the analogous Diels−Alder reaction of diene 12 , i.e., at 155 vs 100 °C.…”

Section: Resultsmentioning

confidence: 99%

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Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones

et al. 2009

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Violet smelling ionones 1-3, occurring in the headspace of different flowers, are well-known perfumery raw materials. With the goal to recognize the still ill-defined spatial arrangement of structural features relevant to the binding of ionones to olfactory G-protein coupled receptors, through B3LYP/6-31G(d) modeling studies we identified bicyclic compounds 7-9 as conformationally constrained 13-alkyl-substituted analogues of monocyclic alpha- and gamma-ionones. They were thus synthesized to evaluate the olfactory properties. The enantioselective syntheses of 7-9 entailed two common key steps: (i) a Diels-Alder reaction to construct the octalinic core and (ii) a Julia-Lythgoe olefination to install the alpha,beta-enone side chain. The odor thresholds of synthetic 7 and 9 were significantly lower than the corresponding parent ionones, and 9 showed the lowest threshold value among violet-smelling odorants examined so far. Modeling studies suggested a nearly identical spatial orientation of key hydrophobic and polar moieties of compounds 1, 3, and 4-9. Presumably, interaction of these moieties with ionone olfactory receptors (ORs) triggers a similar receptor code that is ultimately interpreted by the human brain as a pleasant woody-violet smell. These results open the way to studies aimed at identifying and modeling complementary binding sites on alpha-helical domains of ionone receptor proteins.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones

et al. 2009

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“…6 They demonstrated that alcohol 14 could be hydrated in such a way to afford triol 15 in modest yield. This was a significant achievement as it completed the critical cis -decalin ring fusion of vinigrol.…”

Section: Introductionmentioning

confidence: 99%

Synthetic approaches and total syntheses of vinigrol, a unique diterpenoid

Draghici

Njardarson

2015

Tetrahedron

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This review summarizes all published total and formal syntheses as well as synthetic approaches towards vinigrol. The content is divided into sections, which are focused on each research groups contributions and how far each approach was advanced towards vinigrol. Graphical summaries of all the published vinigrol structural perspectives, starting materials used for each routes and a discussion of preferred or privileged reactions employed is also presented.

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The Barton‐McCombie Reaction

2012

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Deoxygenations of alcohols, i.e., processes that replace a hydroxyl group with hydrogen at a saturated carbon, find applications in both total synthesis and the systematic modifications of natural products. They may also be employed to introduce deuterium or tritium in a site‐specific manner. Reductive methods that involve ionic or highly polarized reagents or intermediates can be limited in their applicability: for example, competing reaction pathways including cationic rearrangements and anionic eliminations may be encountered in sterically hindered systems with substrates bearing heteroatoms close to the center undergoing reduction. As evidenced by developments over the last few decades, methods that involve the generation and direct quenching via hydrogen atom abstraction of the derived, carbon‐centered radical typically show the greatest tolerance for the presence of other functional groups and for variations in both the steric acid and the electronic environment in the vicinity of the center undergoing deoxygenation. Derivatization of the hydroxyl is a prerequisite, the determinant factors for efficient formation of the deoxygenated product lies in the ability of the combination of the substrate and reagents to induce homolysis of the C‐O bond coupled with the induction of homolysis to rapidly reduce a free radical by hydrogen donation, thereby propagating an efficient chain process. A high‐yielding way to realize this sequence was first described by Barton McCombie using the free‐radical chain reaction of O ‐thioacyl derivatives of secondary alcohols with tri‐ n ‐butylstannane. This chapter provides a detailed description and comparison of the combinations of substrates and reagents that will bring about these processes and provides a summary and evaluation of alternative deoxygenation methods. Mechanistic and stereochemical issues set out the scope and limitations of these processes with respect to both the thioacylation and reduction steps and exemplify some applications to both total synthesis and the modification of natural products.

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Studies toward the Synthesis of Vinigrol. First Construction of the Tricyclic Ring System

Cited by 39 publications

References 22 publications

Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones

Enantioselective Synthesis and Olfactory Evaluation of Bicyclic α- and γ-Ionone Derivatives: The 3D Arrangement of Key Molecular Features Relevant to the Violet Odor of Ionones

Synthetic approaches and total syntheses of vinigrol, a unique diterpenoid

The Barton‐McCombie Reaction

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