Stereoselective synthesis of (2S,3S,7S)-3,7-dimethylpentadecan-2-ol and its propionate, the sex pheromones of pine sawflies

Kovalenko, V. N.; Matiushenkov, Evgenii A.

doi:10.1016/j.tetasy.2012.09.002

Cited by 6 publications

(9 citation statements)

References 40 publications

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“…[1][2][3][4][5][6][7][8][9][10][11] These compounds are excellent building blocks due to their availability in high enantiomeric purity, simple techniques of preparation, and a substantial synthetic potential of the cyclopropane ring. [12][13][14][15] For example, they were utilized in the asymmetric synthesis of pyrethroids 1,2 and other natural products, 3,4 stereoregular oligocyclopropanes, 5 chiral biaryls, 6 and liquid crystals.…”

Section: Introductionmentioning

confidence: 99%

“…10 Further, the chiral acid (1R,3S)-1 was used in the construction of the methyl branched chain of the pine sawfly sex pheromone. 11 β-Halogen atoms in esters, amides or nitriles of 1 may easily be substituted with nucleophiles and this property gives an additional method of functionalization of cyclopropane compounds. 16,17 These transformations could proceed with preservation or cleavage of the cyclopropane ring, depending on the nature of the nucleophilic reagent.…”

Section: Introductionmentioning

confidence: 99%

“…[16][17][18][19][20] Recently, numerous examples of stereoselective substitution in monobromocyclopropanes with heteroatomic nucleophiles have been described. 21,22 In continuation of our research, 10,11 the substitution of halogens by thiophenoxy groups in the chiral acids 1 has become the object of investigation. The stereochemistry of the dithiocyclopropanes obtained and the process of the cyclopropane ring opening were studied.…”

Section: Introductionmentioning

confidence: 99%

“…Finally, the process of the ring cleavage of dithiocyclopropanes obtained was investigated, because the derivatives of acids 5, as well as acids 1, could be the precursors of useful 1,4-bifunctional chiral compounds with an isopentane skeleton. 10,11 Ester (1RS,3S)-4, as described above, demonstrates high stability during long-term heating under basic conditions (Scheme 1), but similar gem-diphenylthiocyclopropyl ketones are known to be easily transformed into S-phenylalkanethioate or ketene diphenylthioacetals under acidic catalysis. 23,24 The experiments showed that ester (1RS,3S)-4 was unreactive in aqueous formic acid and even in a refluxing mixture of acetone and hydrochloric acid.…”

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confidence: 99%

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Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Kovalenko¹

2013

Arkivoc

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Substitution of the β-halogen atoms in methyl (1R,3S)-2,2-dichloro-3-methylycyclopropanecarboxylate with sodium thiophenolate leads to the di(phenylthio) ester (1RS,3S)-4 as a mixture of diastereomers. The cis-trans isomerisation of methyl (1RS,3S)-3-methyl-2,2-bis(phenylthio)-cyclopropanecarboxylate 4, basic hydrolysis and subsequent crystallization gave the corresponding acid (1R,3S)-5 in high diastereomeric and enantiomeric purity. On the other hand, ring opening of the ester (1RS,3S)-4 under acidic conditions leads to methyl 3-methyl-4,4-di(phenylthio)prop-3-enoate (8) or the chiral S-phenyl thioester methyl (3S)-3-methyl-4-oxo-4-(phenylthio)butanoate (7).

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

mentioning

confidence: 99%

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Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Kovalenko¹

2013

Arkivoc

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“…[1][2][3] Some alcohols can be dinitrobenzoylated to improve their diastereomeric or enantiomeric purities by recrystallization. [4][5][6][7][8] The resulting dinitrobenzoates are usually deacylated by alkaline solvolysis (a methanolic solution of K 2 CO 3 or aqueous KOH). [4][5][6][7][8] 3,5-Dinitrobenzoic acid has been used as a pro-nucleophile in the original Mitsunobu reaction 9) and the catalytic Mitsunobu reaction.…”

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confidence: 99%

Versatile Amine-Promoted Mild Methanolysis of 3,5-Dinitrobenzoates and Its Application to the Synthesis of Colorado Potato Beetle Pheromone

Yamano

Sasaki

Wada

2017

CHEMICAL & PHARMACEUTICAL BULLETIN

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A mild deacylation method for 3,5-dinitrobenzoates using methanolic solutions of amines, such as dialkylamines, was developed. The method's versatility was confirmed by applying it to synthesizing a key intermediate for Colorado potato beetle pheromone.Key words 3,5-dinitrobenzoate; amine-promoted methanolysis; selective deacylation; Colorado potato beetle pheromone 3,5-Dinitrobenzoates are typically crystalline compounds and are often used to confirm the structures of alcohols by X-ray crystallography.1-3) Some alcohols can be dinitrobenzoylated to improve their diastereomeric or enantiomeric purities by recrystallization. [4][5][6][7][8] The resulting dinitrobenzoates are usually deacylated by alkaline solvolysis (a methanolic solution of K 2 CO 3 or aqueous KOH). [4][5][6][7][8] 3,5-Dinitrobenzoic acid has been used as a pro-nucleophile in the original Mitsunobu reaction 9) and the catalytic Mitsunobu reaction. 10,11) Thus, a mild deacylation method for dinitrobenzoates would be useful for synthesizing compounds such as natural products and biologically active compounds.Recently, we found that methanolysis of the 3,5-dinitrobenzoate quickly proceeds in the presence of triethylamine in the total synthesis of lycopene-5,6-diols.8) Kobayashi and Acharya,12) and Tonoi et al. 13) reported that the dinitrobenzoates obtained by the Mitsunobu inversion of a secondary alcohols bearing macrocyclic lactone moieties were deacylated by treatment with a methanolic solution of triethylamine. These reports encouraged us to investigate versatility of this reaction. In the present work, we investigated the alcoholysis of dinitrobenzoates in the presence of various amines. Then, we applied our mild deacylation method in the efficient asymmetric synthesis of Colorado potato beetle (CPB) pheromone 14) and its enantiomer. Results and DiscussionAmine-Promoted Methanolysis of 3,5-Dinitrobenzoates The time course of the methanolysis in the presence of triethylamine (0.2-1.0 eq) of 3,5-dinitrobenzoate 3, which was prepared from previously synthesized compound 1 15) (Chart 1), was monitored by HPLC ( Fig. 1(a)). The conversions (%) of starting dinitrobenzoate 3 into alcohol 2 were calculated based on the peak areas and molar absorbance coefficients (ε) of 2 (2550) and 3 (9970) at a detection wavelength of 254 nm. The reaction proceeded even in the presence of a catalytic amount of triethylamine and the reaction rate increased with the molar equivalents of the amine. Next, we investigated the methanolysis of 3 in the presence of 0.5 eq of other amines (Fig. 1(b)). Reaction rates of ethylamine, diethylamine and diisopropylamine were almost identical, and those of ammonia, triethylamine, 4-dimethylaminopyridine (DMAP) followed in this order. Methanolysis of 3 with 0.2 eq of diethylamine completed with a bit slower rate (99%: 4h) than that of 0.5 eq (99%: 1.5 h). Interestingly, the rate of ethanolysis of 3 was much lower than that of methanolysis. A 1-mmol-scale methanolysis of 3 with 0.5 eq of diethylamine provided alcohol 2 in nearly ...

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Emergence of Copper‐Mediated Formation of C–C Bonds

2016

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Copper‐catalyzed cross‐coupling reactions have found widespread application in carbon–carbon or carbon–heteroatom bond formation. The relatively low toxicity, ease of handling, and low cost of these versatile complexes make them attractive for the elaboration of new methodologies and for the obtaining of new compounds. We focus on recent methods for the copper‐mediated formation of carbon–carbon bonds illustrated by different coupling reactions: cross‐dehydrogenative coupling, decarboxylative cross‐coupling, Sonogashira‐type reactions, Suzuki‐type reactions, and Neigishi‐type reactions. Domino reactions and, finally, more atypical reactions are also illustrated.

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Stereoselective synthesis of (2S,3S,7S)-3,7-dimethylpentadecan-2-ol and its propionate, the sex pheromones of pine sawflies

Cited by 6 publications

References 40 publications

Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Chiral methyl trans-2,2-dichloro-3-methylcyclopropanecarboxylate upon exposure to thiophenolate nucleophile

Versatile Amine-Promoted Mild Methanolysis of 3,5-Dinitrobenzoates and Its Application to the Synthesis of Colorado Potato Beetle Pheromone

Emergence of Copper‐Mediated Formation of C–C Bonds

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