Synthesis of (−)-elemoxide, a commercially important fragrance compound

Rodrigues, Lima; Majik, Mahesh S.; Tilve, Santosh G.; Wahidulla, Solimabi

doi:10.1016/j.tetlet.2018.08.003

Cited by 6 publications

(7 citation statements)

References 16 publications

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“…The i -propenyl group at C-5 was selectively converted into the corresponding epoxide using m -CPBA/CH 2 Cl 2 /0 °C, and the epoxy ring was oxidatively cleaved with H 5 IO 6 /Et 2 O to give ketone 48 along with a small amount of aldehyde 49 .…”

Section: Resultsmentioning

confidence: 99%

“…Later, we found that the amount of LiCl used in the reaction had a critical effect on the formation of 47; when no more than 1.5 mol equivalent of LiCl was added to the reaction system, only 46 (57%) was formed. 42 The i-propenyl group at C-5 was selectively converted into the corresponding epoxide using m-CPBA/CH 2 Cl 2 /0 °C, 43 and the epoxy ring was oxidatively cleaved with H 5 IO 6 /Et 2 O 44 to give ketone 48 along with a small amount of aldehyde 49.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…MS (EI) m/z (%): 438 (M + , 1), 423 (70), 395 (30), 381 (15), 305 (20), 291 (100), 265 (20), 217 (25); HRMS (EI) m/z: M + calcd for C 25 H 50 O 2 Si 2 ,438.3344;found,438.3340. (1S,2S,4S,6R,8S,nonane (43). Compound 40 (16 mg, 0.044 mmol) was added to a solution of MoO 2 (acac) 2 in ethereal H 2 O 2 (0.4 mL, with the stock solution prepared by dissolving 1.8 mg of MoO 2 (acac) 2 in 0.8 mL of ethereal H 2 O 2 ).…”

Section: -((1s2s3r5s7s)-3-((tert-butyldimethylsilyl)oxy)-5-isopropyl-...mentioning

confidence: 99%

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Enantioselective Total Synthesis of 10-Desoxy Analogue of a Previously Reported Natural Peroxyguaidiol

Zha

2022

J. Org. Chem.

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Described herein is an enantioselective synthesis of an analogue of a previously reported guaiane endoperoxide isolated from aerial parts of Croton arboreous. The polycyclic framework of the target structure was constructed with the C-7 stereogenic center derived from L-(−)-carvone and other stereogenic centers installed via substrate chirality-induced asymmetric reactions, starting with the synthesis of the seven-membered ring through regioselective enolization of carvone, ring-expansion, and installation of a conjugated C�C bond. Further functionalization was then achieved through regioselective enolization, triflation, and installation of an isopropenyl group. During the synthesis, some exceptions to the well-known rules of "thermodynamic control" and "kinetic control" in enolization of asymmetric cyclic ketones were observed. In construction of the bridged five-membered and endoperoxy rings, a peroxycarbenium [3 + 2] cycloaddition reaction with alkenes was carried out with several alkenes-silyl-gemdihydroperoxides of different relative configurations. However, no expected [3 + 2] products were observed. Finally, the fivemembered ring was smoothly installed through an intramolecular Darzens reaction, and the peroxy functionality was introduced via a carbon-centered radical-mediated reaction with triplet oxygen, followed by an intramolecular etherification under acidic conditions. Comparison of the 1 H and 13 C NMR spectra of the synthetic analogue and the natural product revealed that the latter was definitely not an endoperoxide.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: -((1s2s3r5s7s)-3-((tert-butyldimethylsilyl)oxy)-5-isopropyl-...mentioning

confidence: 99%

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Enantioselective Total Synthesis of 10-Desoxy Analogue of a Previously Reported Natural Peroxyguaidiol

Zha

2022

J. Org. Chem.

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“…O citronelol, um composto abundante no óleo essencial de C. winterianus, possui atividade neuroprotetora e anticonvulsiva (Sousa et al, 2006), anti-inflamatória (Zhuang et al, 2009) e analgésica (Brito et al, 2012). O limoneno, presente em maior Research, Society and Development, v. 9, n. 11, e4359119959, 2020 (CC BY 4.0) | ISSN 2525-3409 | DOI: http://dx.doi.org/10.33448/rsd-v9i11.9959 concentração na Comercial 2, o que pode gerar um diferencial no aroma deste óleo e o elemol, que também é um composto com atividade repelente, potencializando os efeitos do citronelal (Carroll et al, 2010), utilizado na síntese de fragrâncias para a indústria (Rodrigues et al, 2018), sendo também um redutor de lesões de pele e anti-inflamatório (Yang et al, 2015).…”

Section: Resultsunclassified

Determinação dos índices físico-químicos dos óleos essenciais de Rosmarinus officinalis, Cymbopogon citratus e Cymbopogon winterianus

Carreiro

Rahal

Bortolucci

et al. 2020

RSD

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O controle de qualidade em óleos essenciais é de grande importância para evitar adulterações destes produtos, porém são escassas informações sobre as características físico-químicas. Desta forma, o objetivo deste trabalho foi realizar análises físico-químicas de óleos essenciais de Rosmarinus officinalis, Cymbopogon citratus e Cymbopogon winterianus. Os óleos foram obtidos de dois fornecedores comerciais e codificados como Comercial 1 e 2. Estes óleos foram comparados com óleos extraídos por hidrodestilação de folhas das plantas implantadas no Horto Medicinal da Universidade e codificados como Cultivada. Os óleos foram obtidos pelo processo de hidrodestilação durante 3 horas para o R. officinalis e de 2 horas para C. citratus e C. winterianus. Foram determinados a densidade absoluta (g/mL), o índice de refração e a composição química (CG/EM) dos óleos. Para a densidade e o índice de refração os resultados indicaram não haver diferenças entre as amostras comerciais e cultivada, entretanto na composição química observou-se diferenças entre os compostos majoritários. No óleo de alecrim destacou-se o 1,8-cineol com 5,82% (Cultivada), 17,28% (Comercial 1) e 27,42% (Comercial 2). No óleo essencial de capim limão o mirceno apresentou 8,52% (Cultivada) e ausência nas amostras de ambos os fornecedores comerciais. No óleo essencial de citronela o limoneno encontra-se com 9,55% (Comercial 2), 2,31% (Comercial 1) e 3,62% (Cultivada), indicando que a variação do percentual de compostos entre as amostras podem ter sido ocasionadas principalmente por fatores abióticos e bióticos, pois as amostras provêm de culturas implantadas em locais diferentes, interferindo nas características destes óleos essenciais.

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“…In 2018, Majik et al reported a semi-synthesis of (−)-elemoxide [ 127 ] ( Scheme 11 b), a sesquiterpene oxide with scents of rhubarb, laurel and thyme. The route of synthesis started with the regioselective epoxidation of natural extracted (−)-elemol, with subsequent reductive ring-opening.…”

Section: Synthesis Of Heterocyclic Fragrances Via Addition-type React...mentioning

confidence: 99%

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

Lin¹,

Huang²,

Ouyang³

et al. 2022

Molecules

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With increasing demand for customized commodities and the greater insight and understanding of olfaction, the synthesis of fragrances with diverse structures and odor characters has become a core task. Recent progress in organic synthesis and catalysis enables the rapid construction of carbocycles and heterocycles from readily available unsaturated molecular building blocks, with increased selectivity, atom economy, sustainability and product diversity. In this review, synthetic methods for creating cyclic fragrances, including both natural and synthetic ones, will be discussed, with a focus on the key transformations of alkenes, alkynes, dienes and enynes. Several strategies will be discussed, including cycloaddition, catalytic cyclization, ring-closing metathesis, intramolecular addition, and rearrangement reactions. Representative examples and the featured olfactory investigations will be highlighted, along with some perspectives on future developments in this area.

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Synthesis of (−)-elemoxide, a commercially important fragrance compound

Cited by 6 publications

References 16 publications

Enantioselective Total Synthesis of 10-Desoxy Analogue of a Previously Reported Natural Peroxyguaidiol

Enantioselective Total Synthesis of 10-Desoxy Analogue of a Previously Reported Natural Peroxyguaidiol

Determinação dos índices físico-químicos dos óleos essenciais de Rosmarinus officinalis, Cymbopogon citratus e Cymbopogon winterianus

Synthesis of Cyclic Fragrances via Transformations of Alkenes, Alkynes and Enynes: Strategies and Recent Progress

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