A short synthesis of the monoterpenes (−)‐6α‐hydroxy‐ carvotanacetone and (−)‐6β‐hydroxycarvotanacetone from (<i>R</i>)‐(−)‐carvone

Santos, Reginaldo Bezerra dos; Zanotto, Paulo R.; Brocksom, Timothy J.; Brocksom, Ursula

doi:10.1002/ffj.1001

Cited by 11 publications

(9 citation statements)

References 8 publications

(5 reference statements)

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“…Monoterpenes and their functionalized derivatives are widely used as substrates for the preparation of novel semi‐synthetic compounds with pharmacological and olfactory properties . Both isomers of carvone occur widely in nature.…”

Section: Introductionmentioning

confidence: 99%

Synthesis and olfactory evaluation of homologous series of (+)‐ and (−)‐carvone oxime ethers

Strub

Kula

Sikora

et al. 2015

Flavour & Fragrance J

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Novel semi‐synthetic fragrant compounds were prepared from both isomers of carvone. Deprotonation of (+) and (−)‐carvone oximes with sodium hydride and subsequent O‐Alkylation with various alkyl halides in DMSO resulted in 18 ethers. Scents of most synthesized compounds are agreeable. A shift of fragrance is observed between substrates. The scent of (−)‐carvone resembles that of spearmint and (+)‐carvone – caraway. The fragrance of carvone oximes is similar, vegetable‐like. Significant differences were observed between homologous series of carvone oxime ethers. Their odours range from vegetable‐like (pickled cucumber, leaves of horseradish and carrot, scallion and onion) and herbaceous to sulphuric, floral (lily) and fruity (blackcurrant and pear). Copyright © 2015 John Wiley & Sons, Ltd.

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Section: Introductionmentioning

confidence: 99%

Synthesis and olfactory evaluation of homologous series of (+)‐ and (−)‐carvone oxime ethers

Strub

Kula

Sikora

et al. 2015

Flavour & Fragrance J

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“…In this work we examined the possibility for oxygenation of (R)-(-)-carvone at C 6 according to Rubottom (transformation of ketone into α-hydroxy ketone through silyl enol ether, followed by epoxidation and rearrangement) [6,7] and oxidative cleavage of the resulting hydroxy ketones with Pb(OAc) 4 . α-Hydroxylation of ketones of the carvone series was reported previously, namely carvotanacetone (I) was oxidized to stereoisomeric 6-hydroxy derivatives IIa and IIb [8] (Scheme 1).…”

mentioning

confidence: 71%

“…(5R,6R)-and (5R,6S)-6-Hydroxy-5-isopropenyl-2-methylcyclohex-2-en-1-ones IVa and IVb were synthesized according to the procedure described in [8] and were isolated as oily liquids with an overall yield …”

Section: Methodsmentioning

confidence: 99%

Synthesis of 6-hydroxycarvone derivatives and their oxidative decyclization with lead tetraacetate

et al. 2011

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“…We also failed to perform the oxidative cleavage of epoxyalcohol IV by treating with HIO 4 , we obtained only diol V. At the reduction of epoxyalcohol IV with LiAlH 4 Thus except for the reduction of the epoxyketone I with sodium borohydride into alcohol IV the other reactions of these compounds proceeded by unexpected routes or with the partial formation of abnormal products.…”

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confidence: 92%

Influence of steric factors on the direction of reactions

et al. 2011

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Sterical loading, topology, and the character of the organic molecule functionalization sometimes lead to the "uncommon" course of typical reactions with its participation. One of such compounds is epoxycyclohexanone I that we have recently described [1].Our attempts to convert it into hydroxycyclohexanone II by ozonolysis under the conditions of Criegee rearrangement [2, 3] resulted only in diketone III [1] inert with respect to m-chloroperbenzoic acid. We also failed to perform the oxidative cleavage of epoxyalcohol IV by treating with HIO 4 , we obtained only diol V. At the reduction of epoxyalcohol IV with LiAlH 4 alongside the expected diol VI we isolated regioisomeric diols VII and O O O OH O O O O O 3 I II III HO O IV NaBH 4 HO OH V HIO 4 THF _ H 2 O m-ClC 6 H 4 CO 3 H VIII. Usually the reduction with LiAlH 4 of trisubstituted epoxides provides a tertiary alcohol. The assignment of stereoisomeric diols VII and VIII was done based on the characteristic doublets of H 3 in the 1 H NMR spectra. Whereas for 2,3-trans-isomer VII J 3,2 is 11.2 Hz [δ(H 3 ) 3.30 ppm], in the isomer VIII J 3,2 is 5.2 Hz [δ(H 3 ) 3.51 ppm] (analogous examples have been described in [4]). For further identifi cation diol VIII was converted into diacetate IX. HO OH VI, 33% IV HO OH HO VII, 27% VIII, 7% OH AcO OAc Ac 2 O _ Py IX + LiAlH 4 THF, Δ +Thus except for the reduction of the epoxyketone I with sodium borohydride into alcohol IV the other reactions of these compounds proceeded by unexpected routes or with the partial formation of abnormal products.(1R,3R,5S)-4,4-Dimethyl-5-isopropenyl-2-methylidenecyclohexane-1,3-diol (V). To a solution of 0.08 g (0.41 mmol) of compound IV in 5 ml of the mixture

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A short synthesis of the monoterpenes (−)‐6α‐hydroxy‐ carvotanacetone and (−)‐6β‐hydroxycarvotanacetone from (R)‐(−)‐carvone

Cited by 11 publications

References 8 publications

Synthesis and olfactory evaluation of homologous series of (+)‐ and (−)‐carvone oxime ethers

Synthesis and olfactory evaluation of homologous series of (+)‐ and (−)‐carvone oxime ethers

Synthesis of 6-hydroxycarvone derivatives and their oxidative decyclization with lead tetraacetate

Influence of steric factors on the direction of reactions

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