A New Biomimetic‐Like Aromatization of the Cyclic End Groups of Terpenoids with Stereospecific Migration of One of the Methyl Groups: A Convenient Route to Isorenieratene (ϕ,ϕ‐Carotene)

Valla, Alain; Andriamialisoa, Zo; Valla, Benoist; Labia, Roger; Guillou, Régis Le; Dufossé, Laurent; Cartier, Dominique

doi:10.1002/ejoc.200600794

Cited by 10 publications

(9 citation statements)

References 23 publications

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“…Ketone 4 , which is a natural product with a pleasant floral scent, was previously synthesized by the palladium‐catalyzed arylation of 2,3,6‐trimethylbromobenzene with 3‐butene‐2‐one . A few examples in the literature have shown that ketone 4 can also be formed directly from ionones . The microbial oxidation of β‐ionone gave compound 4 in minor amounts, along with acetate 3 (in 1–2 % yield each) .…”

Section: Resultsmentioning

confidence: 99%

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Aerobic Palladium‐Catalyzed Oxidations in the Upgrading of Biorenewables: Oxidation of β‐Ionone and α‐Ionone

2017

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α‐Ionone and β‐ionone are natural products that are found in a variety of essential oils and are also produced synthetically on an industrial scale. Both ionones were selectively oxidized by molecular oxygen in the presence of chloride‐free Pd(OAc)2/para‐benzoquinone catalytic systems. Highly functionalized oxygenated terpenoids that were obtained in these new processes are potentially useful as ingredients in synthetic perfumes, cosmetics, and pharmaceuticals. β‐Ionone (known as rose ketone) was converted into a single major product, whereas α‐ionone gave three isomeric products, all of which resulted from the allylic oxidation of their endocyclic double bonds. These processes operated with an efficient dioxygen‐coupled catalytic turnover under 5–10 atm pressure, in the absence of conventionally used metal‐redox‐active cocatalysts. Alternatively, the reactions could be efficiently conducted under atmospheric pressure in the presence of copper acetate to assist in the regeneration of BQ by molecular oxygen.

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Section: Resultsmentioning

confidence: 99%

“…The microbial oxidation of β‐ionone gave compound 4 in minor amounts, along with acetate 3 (in 1–2 % yield each) . More recently, compound 4 was obtained in up to 65 % yield through the stoichiometric oxidation of α‐, β‐, or retro‐ionone with CuCl 2 , FeCl 3 , or substituted BQ (2,3‐dichloro‐5,6‐dicyano‐1,4‐benzoquinone) …”

Section: Resultsmentioning

confidence: 99%

Aerobic Palladium‐Catalyzed Oxidations in the Upgrading of Biorenewables: Oxidation of β‐Ionone and α‐Ionone

2017

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“…Methyl migration and aromatization of conjugate carotenoid systems is important in the biosynthesis of aromatic carotenoids 19 and the same rearrangement can be accomplished by reacting -ionone with 2-4 equivalents CuCl2 (30%) in DMF as solvent, albeit in low yields. 20 It is likely that any build-up of Cu[TPMA]Cl2 in our reaction is responsible for this migration.…”

Section: Scheme 5 Cyclization Of Dienamide 25amentioning

confidence: 94%

Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatization

Geden

Clark

Coles

et al. 2016

Tetrahedron Letters

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(2016) Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides : regiochemistry, indigoid formation and methyl migration-aromatization. Tetrahedron Letters, 57. pp. 3109-3122. Permanent WRAP URL:http://wrap.warwick.ac.uk/81168 Copyright and reuse:The Warwick Research Archive Portal (WRAP) makes this work by researchers of the University of Warwick available open access under the following conditions. Copyright © and all moral rights to the version of the paper presented here belong to the individual author(s) and/or other copyright owners. To the extent reasonable and practicable the material made available in WRAP has been checked for eligibility before being made available.Copies of full items can be used for personal research or study, educational, or not-for-profit purposes without prior permission or charge. Provided that the authors, title and full bibliographic details are credited, a hyperlink and/or URL is given for the original metadata page and the content is not changed in any way. A note on versions:The version presented here may differ from the published version or, version of record, if you wish to cite this item you are advised to consult the publisher's version. Please see the 'permanent WRAP URL' above for details on accessing the published version and note that access may require a subscription.For more information, please contact the WRAP Team at: wrap@warwick.ac.uk Graphical AbstractTo create your abstract, type over the instructions in the template box below. Fonts or abstract dimensions should not be changed or altered.Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatisation Joanna V. Geden, Andrew J. Clark , Stuart R. Coles, Collette S. Guy, Franco Ghelfi and Stephen Thom Leave this area blank for abstract info. Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatization.

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“…Spectra in accordance with those described in the literature. 28 To a stirring solution of methyl 2-cyano-3-methylbut-2-enoate (1.36 g, 9.7 mmol, 1 equiv) and acetic anhydride (0.18 mL, 1.9 mmol, 0.2 equiv) in anhydrous toluene (10 mL) was added DMF-DMA (1.6 mL, 11.7 mmol, 1.2 equiv).…”

Section: Methyl (4e)-2-cyano-5-(dimethylamino)-3-methylpenta-24-dienmentioning

confidence: 99%

Synthesis and Reactivity Profile of Ylidenemalononitrile Enamines and Their Ester Analogs Towards Electrophiles and Nucleophiles

2015

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Herein, we describe the synthesis and reactivity of enamines derived from ylidenemalononitriles and ylidenecyanoacetates. The enamine scope was expanded by (1) increasing yields of aldehyde-derived ylidenemalononitriles, (2) incorporating silyl functionalities, and (3) using other amide acetals to expand the substitution patterns of pyridines resulting from enamine cyclization. In addition, methods to produce α-pyrones and polysubstituted pyridines from both ylidenemalononitriles and ylidenecyanoacetates are described.

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A New Biomimetic‐Like Aromatization of the Cyclic End Groups of Terpenoids with Stereospecific Migration of One of the Methyl Groups: A Convenient Route to Isorenieratene (ϕ,ϕ‐Carotene)

Cited by 10 publications

References 23 publications

Aerobic Palladium‐Catalyzed Oxidations in the Upgrading of Biorenewables: Oxidation of β‐Ionone and α‐Ionone

Aerobic Palladium‐Catalyzed Oxidations in the Upgrading of Biorenewables: Oxidation of β‐Ionone and α‐Ionone

Copper mediated cyclization of 1-substituted enamides, dienamides and trienamides: regiochemistry, indigoid formation and methyl migration-aromatization

Synthesis and Reactivity Profile of Ylidenemalononitrile Enamines and Their Ester Analogs Towards Electrophiles and Nucleophiles

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