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Enantioselective Bioreduction of 5-Hexen-2-one in Directional Synthesis of Insect Pheromones

  • Organic Synthesis and Industrial Organic Chemistry
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Abstract

(2S)-Tridecyl acetate (sex pheromone of Drosophila mulleri) and (S)-1-methylbutyl esters of (2Е)-2-methylpent-2-enoic and (2Е)-2,4-dimethylpent-2-enoic acids (components of aggregation pheromone of Rhyzopertha dominica lesser grain borer) were synthesized from commercially available 5-hexen-2-one (allylacetone) in overall yields of 31.0, 28.8, and 29.2%, respectively, based on the starting ketone. The key steps of the process were enantioselective bioreduction of 5-hexen-2-one with cells of Rhodococcus erythropolis А-25 actinobacteria to (S)-5-hexen-2-ol in 77% yield (ее 98.4%) and the following chemoselective reactions: ozonolytic cleavage of (S)-5-hexen-2-yl acetate, followed by reduction of the peroxy products with NaBH4 to (S)-5-hydroxypent-2-yl acetate in 88% yield; transformation of (S)-4-acetoxy-1-tosyloxypentane into (2S)-tridecyl acetate in 58% yield by dilithium tetrachlorocuprate catalyzed cross-coupling with the Grignard reagent derived from n-octyl bromide; and reduction of both ester groups in the tosylate with lithium aluminum hydride to (S)-pentan-2-ol (yield 79%), followed by its esterification with (2Е)-2-methylpent-2-enoyl or (2Е)-2,4-dimethylpent-2-enoyl chloride with 68 and 69% yields, respectively.

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ACKNOWLEDGMENTS

Equipment of the Chemistry Center for Shared Use, Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences was used in the study.

Funding

The study was financially supported by the Fundamentals of Chemistry program of the Russian Academy of Sciences, theme: Directional Synthesis of Low-Molecular-Mass Bioregulators, Based on Selective Transformations of Lipids, Terpenoids, and Steroids (state registry no. 122031400275-1), and by the Ministry of Science and Higher Education of the Russian Federation within the framework of the base part of the government assignment in the field of scientific activity (no. 4.6451.2017/8.9), theme: Regio- and Stereoselective Synthesis Functional Organic Compounds, Based on Bio- and Coordination Catalytic Systems and Available Petrochemical and Vegetable Feedstock (state registry no. 4.6451.2017/BCh, 2017).

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Authors and Affiliations

  1. Ufa State Petroleum Technical University, Ufa, 450062, Bashkortostan, Russia

    N. I. Petukhova, V. V. Zorin, A. R. Sakaeva & A. V. Mityagina

  2. Ufa Institute of Chemistry, Ufa Federal Research Center, Russian Academy of Sciences, Ufa, 450054, Bashkortostan, Russia

    E. R. Nurieva, V. A. Vydrina, M. P. Yakovleva & G. Yu. Ishmuratov

Authors
  1. N. I. Petukhova
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  2. V. V. Zorin
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  3. A. R. Sakaeva
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  4. A. V. Mityagina
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  5. E. R. Nurieva
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  6. V. A. Vydrina
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  7. M. P. Yakovleva
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  8. G. Yu. Ishmuratov
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Contributions

G.Yu. Ishmuratov and V.V. Zorin: development of the stereoselective synthesis strategy, task setting; V.A. Vydrina and M.P. Yakovleva: development of the experimental procedure, collection of published data, and preparation of the literature review; V.A. Vydrina and E.R. Nurieva: synthesis and NMR study of the samples; N.I. Petukhova, A.V. Mityagina, and A.R. Sakaeva: biocatalyst preparation and reduction of 5-hexen-2-one to (S)-5-hexen-2-ol using microorganism cells.

Corresponding authors

Correspondence to N. I. Petukhova or G. Yu. Ishmuratov.

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The authors declare that they have no conflict of interest.

Additional information

Translated from Zhurnal Prikladnoi Khimii, No. 3, pp. 389–398, March, 2022 https://doi.org/10.31857/S0044461822030124

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Petukhova, N.I., Zorin, V.V., Sakaeva, A.R. et al. Enantioselective Bioreduction of 5-Hexen-2-one in Directional Synthesis of Insect Pheromones. Russ J Appl Chem 95, 442–450 (2022). https://doi.org/10.1134/S1070427222030156

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