Skip to main content
SpringerLink
Log in

Transformations of Seven-Membered Terpene Lactones toward Low-Molecular-Weight Bioregulators

  • Published:
Russian Journal of Organic Chemistry Aims and scope Submit manuscript

Abstract

The review describes low-temperature reduction of (–)-mentholactone with diisobutylaluminum hydride in methylene chloride. Depending on the conditions, three products are formed: (2S,4R,7S)-7-isopropyl-4-methyloxepan-2-ol [(–)-mentholactol), (6R)-8-hydroxy-2,6-dimethyloctan-3-one, and (2S,4R,7S)-2-iso­butoxy-7-isopropyl-4-methyloxepane. Possible ways of formation of each product have been proposed, and conditions for their selective formation have been found. The synthesis of oxepan-2-ol isobutyl acetals via low-temperature (–70°C) reduction of 7-membered lactones with diisobutylaluminum hydride in methylene chloride is considered. The synthesis of a number of low-molecular-weight bioregulators, including optically active pheromones of insect pests in agriculture and forestry, based on (–)-mentholactol, its aluminate, and (6R)-8-hydroxy-2,6-dimethyloctan-3-one is discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1.
Fig. 2.
Fig. 3.
Scheme
Fig. 4.
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Fig. 5.
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Fig. 6.
Scheme
Fig. 7.
Fig. 8.
Fig. 9.
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme
Scheme

REFERENCES

  1. Yakovleva, M.P., Denisova, K.S., Vydrina, V.A., Tolstikov, A.G., and Ishmuratov, G.Yu., Russ. J. Org. Chem., 2021, vol. 57, p. 679. https://doi.org/10.1134/S1070428021050018

    Article  CAS  Google Scholar 

  2. Parenty, A., Moreau, X., and Campagne, J.-M., Chem. Rev., 2006, vol. 106, p. 911. https://doi.org/10.1021/cr0301402

    Article  CAS  PubMed  Google Scholar 

  3. Krow, R., Tetrahedron, 1981, vol. 37, p. 2697. https://doi.org/10.1016/S0040-4020(01)92337-3

    Article  CAS  Google Scholar 

  4. Ishmuratov, G.Yu., Vydrina, V.A., Galkina, Yu.A., Yakov­leva, M.P., Ishmuratova, N.M., and Tolsti­kov, A.G., Chem. Nat. Compd., 2015, vol. 51, p. 1011. https://doi.org/10.1007/s10600-015-1483-5

    Article  CAS  Google Scholar 

  5. Shono, T., Matsumura, Y., Hibino, K., and Maya­waki, Sh., Tetrahedron Lett., 1974, vol. 15, p. 1295. https://doi.org/10.1016/s0040-4039(01)82471-0

    Article  Google Scholar 

  6. Ochsner, P.A. and De Polo, K.-F., Swiss Patent no. 12936176, 1979; Ref. Zh., Khim., 1979, no. 20P516.

  7. Daniewski, A.R. and Warchoł, T., Justus Liebigs Ann. Chem., 1992, p. 965. https://doi.org/10.1002/JLAC.1992199201159

  8. Adams, F., Pehl, T.M., Kränzlein, M., Kernbichl, S., Kang, J., Papadakis, C.M., and Rieger, B., Polym. Chem., 2020, vol. 11, p. 4426. https://doi.org/10.1039/d0py00379d

    Article  CAS  Google Scholar 

  9. Wanamaker, C.L., O’Leary, L.E., Lynd, N.A., Hill­myer, M.A., and Tolman, W.B., Biomacromolecules, 2007, vol. 8, p. 3634. https://doi.org/10.1021/bm700699g

    Article  CAS  PubMed  Google Scholar 

  10. Gurusamy-Thangavelu, S.A., Emond, S.J., Kulsh­restha, A., Hillmyer, M., Macosko, C., Tolman, W., and Hove, T., Polym. Chem., 2012, vol. 3, p. 2941. https://doi.org/10.1039/C2PY20454A

    Article  CAS  Google Scholar 

  11. Takahashi, K., Komine, K., Yokoi, Y., Ishihara, J., and Hatakeyama, S., J. Org. Chem., 2012, vol. 77, p. 7364. https://doi.org/10.1021/jo301145r

    Article  CAS  PubMed  Google Scholar 

  12. Burka, L.T., Bowen, R.M., and Wilson, B.J., J. Org. Chem., 1974, vol. 39, p. 3241. https://doi.org/10.1021/jo00936a014

    Article  CAS  PubMed  Google Scholar 

  13. Wuest, J.D., J. Org. Chem., 1977, vol. 42, p. 2111. https://doi.org/10.1021/jo00432a019

    Article  CAS  Google Scholar 

  14. Marx, J.N. and Norman, L.R., J. Org. Chem., 1975, vol. 40, p. 1602. https://doi.org/10.1021/jo00899a018

    Article  CAS  Google Scholar 

  15. Thorel, J.-N., FR Patent no. 2622103 A1, 1989.

  16. Ishmuratov, G.Yu., Yakovleva, M.P., Ganieva, V.A., Gareeva, G.R., Muslukhov, R.R., and Tolstikov, G.A., Chem. Nat. Compd., 2005, vol. 41, p. 549. https://doi.org/10.1007/s10600-005-0203-y

    Article  CAS  Google Scholar 

  17. Lochte, H.L. and Pittman, A.G., J. Org. Chem., 1960, vol. 25, p. 1462. https://doi.org/10.1021/jo01078a620

    Article  CAS  Google Scholar 

  18. Kokke, W.C.M. and Varkevisser, F., J. Org. Chem., 1974, vol. 39, p. 1535. https://doi.org/10.1021/jo00924a018

    Article  CAS  Google Scholar 

  19. Ishmuratov, G.Yu., Yakovleva, M.P., Kharisov, R.Ya., Botsman, L.P., Ishmuratova, N.M., and Tolstikov, G.A., Yubileinyi sbornik “50 let Institutu organicheskoi khimii UNTs RAN” (Jubilee Collection of Papers “50th Anniversary of the Institute of Organic Chemistry, Ufa research Center, Russian Academy of Sciences”), Yunusov, M.S., Ed., Ufa: Gilem, 2001, p. 167.

  20. Safiullin, P.L., Volgarev, A.N., Ishmuratov, G.Yu., Yakovleva, M.P., Odinokov, V.N., Komissarov, V.D., and Tolstikov, G.A., Dokl. Akad. Nauk SSSR, 1991, vol. 316, p. 640.

    Google Scholar 

  21. Vereshchagin, A.N., Kataev, V.E., and Bredinin, A.A., Konformatsionnyi analiz uglevodorodov i ikh proiz­vod­nykh (Conformational Analysis of Hydrocarbons and Their Derivatives), Moscow: Nauka, 1990.

  22. Sandoz, A.G., GB Patent no. 1004661, 1965.

  23. Yakovleva, M.P., Vydrina, V.A., Ishmuratova, N.M., and Ishmuratov, G.Yu., Butlerov. Soobshch., 2021, vol. 65, p. 34. https://doi.org/10.37952/ROI-jbc-01/21-65-2-34

    Article  Google Scholar 

  24. Odinokov, V.N., Ishmuratov, G.Yu., Yakovleva, M.P., Safiullin, R.L., Volgarev, A.N., Komissarov, V.D., Muslukhov, R.R., and Tolstikov, G.A., Dokl. Akad. Nauk SSSR, 1992, vol. 326, p. 842.

    CAS  Google Scholar 

  25. Odinokov, V.N., Ishmuratov, G.Yu., Yakovleva, M.P., Safiullin, R.L., Komissarov, V.D., and Tolstikov, G.A., Russ. Chem. Bull., 1993, vol. 42, p. 1244. https://doi.org/10.1007/BF00702016

    Article  Google Scholar 

  26. Tolstikov, G.A. and Yur’ev, V.P., Alyuminiiorganicheskii sintez (Organoaluminum Synthesis), Moscow: Nauka, 1979.

  27. Ishmuratov, G.Yu., Yakovleva, M.P., Vydrina, V.A., Khasanova, E.F., Muslukhov, R.R., Ishmuratova, N.M., and Tolstikov, G.A., Khim. Rastit. Syr’ya, 2007, p. 23.

  28. Valter, R.E., Kol’chato-tsepnaya izomeriya v organi­cheskoi khimii (Ring–Chain Isomerism in Organic Chemistry), Riga: Zinatne, 1978, p. 170.

  29. Ishmuratov, G.Yu., Yakovleva, M.P., Vydrina, V.A., Muslukhov, R.R., and Talipov, R.F., Vestn. Bashk. Univ., 2008, p. 13.

  30. Ishmuratov, G.Y., Vydrina, V.A., Yakovleva, M.P., Galkina, Yu.A., Muslukhov, R.R., and Tolstikov, G.A., Chem. Nat. Compd., 2012, vol. 47, p. 896. https://doi.org/10.1007/s10600-012-0098-3

    Article  CAS  Google Scholar 

  31. Ishmuratov, G.Y., Vydrina, V.A., Nazarov, I.S., Galki­na, Y.A., Yakovleva, M.P., Lobko, I.F., Muslukhov, R.R., and Tolstikov, A.G., Chem. Nat. Compd., 2013, vol. 48, p. 981. https://doi.org/10.1007/s10600-013-0444-0

    Article  CAS  Google Scholar 

  32. Ishmuratov, G.Yu., Yakovleva, M.P., Ganieva, V.A., Amirkhanov, D.V., and Tolstikov, G.A., Chem. Nat. Compd., 2005, vol. 41, p. 719. https://doi.org/10.1007/s10600-006-0019-4

    Article  CAS  Google Scholar 

  33. Ishmuratov, G.Yu., Yakovleva, M.P., Ishmuratova, N.M., Vydrina, V.A., Muslukhov, R.R., and Tolstikov, G.A., Khim. Interesakh Ustoich. Razvit., 2008, vol. 16, p. 721.

    CAS  Google Scholar 

  34. Ishmuratov, G.Yu., Yakovleva, M.P., Vydrina, V.A., Muslukhov, R.R., and Tolstikov, G.A., Butlerov. Soobshch., 2007, vol. 12, p. 31.

    Google Scholar 

  35. Organic Reactions, Cope, A.C., Ed., New York: Wiley, 1965, vol. 14.

  36. Comprehensive Organic Chemistry, Barton, D. and Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 3.

  37. Li, J.J., Name reactions: A Collection of Detailed Reac­tion Mechanisms, New York: Springer, 2003, 2nd ed.

  38. Ishmuratov, G.Yu., Vydrina, V.A., Yakovleva, M.P., Valeeva, E.F., Muslukhov, R.R., and Tolstikov, G.A., Russ. J. Org. Chem., 2011, vol. 47, p. 1142. https://doi.org/10.1134/S1070428011080045

    Article  CAS  Google Scholar 

  39. Ishmuratov, G.Yu., Yakovleva, M.P., Ishmuratova, N.M., Tolstikov, A.G., and Tolstikov, G.A., Monoterpenoidy v khimii opticheski aktivnykh feromonov nasekomykh (Monoterpenoids in the Chemistry of Optically Active Insect Pheromones), Moscow: Nauka, 2012.

  40. Ishmuratov, G.Yu., Yakovleva, M.P., Kharisov, R.Ya., Muslimova, I.M., Safiullin, R.L., and Tolstikov, G.A., Russ. Chem. Bull., 1997, vol. 46, p. 1033. https://doi.org/10.1007/BF02496144

    Article  CAS  Google Scholar 

  41. Ishmuratov, G.Yu., Yakovleva, M.P., Ganieva, V.A., Kharisov, R.Ya., Gazetdinov, R.R., Abulkaramova, A.M., and Tolstikov, G.A., Chem. Nat. Compd., 2006, vol. 42, p. 92. https://doi.org/10.1007/s10600-006-0043-4

    Article  CAS  Google Scholar 

  42. Yakovleva, M.P., Khasanova, E.F., Vydrina, V.A., Ishmu­ratova, N.M., Talipov, R.F., and Ishmuratov, G.Yu., Vestn. Bashk. Univ., 2008, vol. 13, p. 891.

    Google Scholar 

  43. Ishmuratov, G.Yu., Yakovleva, M.P., Ganieva, V.A., Muslukhov, R.R., and Tolstikov, G.A., Chem. Nat. Compd., 2005, vol. 41, p. 41. https://doi.org/10.1007/s10600-005-0070-6

    Article  CAS  Google Scholar 

  44. Ishmuratov, G.Yu., Kharisov, R.Ya., Yakovleva, M.P., Botsman, O.V., Muslukhov, R.R., and Tolstikov, G.A., Russ. Chem. Bull., Int. Ed., 1999, vol. 48, p. 197. https://doi.org/10.1007/BF02494428

    Article  CAS  Google Scholar 

  45. Ishmuratov, G.Yu., Kharisov, R.Ya., Yakovleva, M.P., Botsman, O.V., Muslukhov, R.R., and Tolstikov, G.A., Russ. J. Org. Chem., 2001, vol. 37, p. 37. https://doi.org/10.1023/A:1012313114674

    Article  CAS  Google Scholar 

  46. Stevens, R.V., Chapman, K.T., Stubbs, C.A., Tam, W.W., and Albizati, K.F., Tetrahedron Lett., 1982, vol. 23, p. 4647. https://doi.org/10.1016/S0040-4039(00)85677-4

    Article  CAS  Google Scholar 

  47. Yoshimoto, H., JP Patent Appl. no. 01261347, 1989; Chem. Abstr., 1990, vol. 112, no. 197633u.

  48. Vydrina, V.A., Kravchenko, A.A., Yakovleva, M.P., Ishmuratova, N.M., and Ishmuratov, G.Yu., Chem. Nat. Compd., 2018, vol. 54, p. 461. https://doi.org/10.1007/s10600-018-2379-y

    Article  CAS  Google Scholar 

  49. Ishmuratov, G.Yu., Vydrina, V.A., Yakovleva, M.P., Valeeva, E.F., Muslukhov, R.R., and Tolstikov, G.A., Russ. J. Org. Chem., 2001, vol. 47, p. 472. https://doi.org/10.1134/S1070428011030304

    Article  CAS  Google Scholar 

  50. Comprehensive Organic Chemistry, Barton, D. and Ollis, W.D., Eds., Oxford: Pergamon, 1979, vol. 6.

  51. Ishmuratov, G.Yu., Vydrina, V.A., Galkina, Yu.A., Yakovleva, M.P., Muslukhov, R.R., and Tolstikov, G.A., Russ. J. Org. Chem., 2014, vol. 50, p. 1704. https://doi.org/10.1134/S1070428014110311

    Article  CAS  Google Scholar 

  52. Suginome, H. and Yamada, S., Bull. Chem. Soc. Jpn., 1985, vol. 58, p. 3055. https://doi.org/10.1246/bcsj.58.3055

    Article  CAS  Google Scholar 

  53. Ishmuratov, G.Yu., Vydrina, V.A., Galkina, Yu.A., Yakovleva, M.P., Kravchenko, A.A., Muslukhov, R.R., and Tolstikov, A.G., Chem. Nat. Compd., 2015, vol. 51, p. 716. https://doi.org/10.1007/s10600-015-1391-8

    Article  CAS  Google Scholar 

  54. Ishmuratov, G.Yu., Vydrina, V.A., Galkina, Yu.A., Yakovleva, M.P., Sabirov, D.Sh., Muslukhov, R.R., Kravchenko, L.V., and Tolstikov, A.G., Russ. J. Org. Chem., 2015, vol. 51, p. 1180. https://doi.org/10.1134/S1070428015080205

    Article  CAS  Google Scholar 

  55. Marell, D.J., Emond, S.J., Kulshrestha, A., and Hoye, T.R., J. Org. Chem., 2014, vol. 79, p. 752. https://doi.org/10.1021/jo402627s

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  56. Vydrina, V.A., Kravchenko, A.A., Sataraev, D.A., Sayakhov, R.R., Yakovleva, M.P., Tolstikov, A.G., and Ishmuratov, G.Yu., Russ. J. Org. Chem., 2020, vol. 56, p. 251. https://doi.org/10.1134/s1070428020020116

    Article  CAS  Google Scholar 

  57. Yakovleva, M.P., Vydrina, V.A., and Ishmuratov, G.Yu., Russ. J. Org. Chem., 2020, vol. 56, p. 1353. https://doi.org/10.1134/S1070428020080047

    Article  CAS  Google Scholar 

  58. Ishmuratov, G.Yu., Vydrina, V.A., Galkina, Yu.A., Yakov­leva, M.P., Kravchenko, A.A., Muslukhov, R.R., and Tolstikov, A.G., Russ. J. Org. Chem., 2015, vol. 51, p. 947. https://doi.org/10.1134/S1070428015070106

    Article  CAS  Google Scholar 

  59. Yakovleva, M.P., Vydrina, V.A., Sayakhov, R.R., and Ish­muratov, G.Yu., Butlerov. Soobshch., 2020, vol. 61, p. 24. https://doi.org/10.37952/ROI-jbc-01/20-61-2-24

    Article  Google Scholar 

Download references

Funding

This work was financially supported by the program of the Russian Academy of Sciences “Target-Oriented Syn­thesis of Low-Molecular-Weight Bioregulators via Selective Transformations of Lipids, Terpenoids, and Steroids” (state registration no. 122031400275-1, 2022).

Author information

Authors and Affiliations

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

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

Authors
  1. V. A. Vydrina
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. M. P. Yakovleva
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. G. Yu. Ishmuratov
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to M. P. Yakovleva.

Ethics declarations

The authors declare the absence of conflict of interest.

Additional information

Translated from Zhurnal Organicheskoi Khimii, 2023, Vol. 59, No. 6, pp. 697–733 https://doi.org/10.31857/S0514749223050010.

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Vydrina, V.A., Yakovleva, M.P. & Ishmuratov, G.Y. Transformations of Seven-Membered Terpene Lactones toward Low-Molecular-Weight Bioregulators. Russ J Org Chem 59, 935–968 (2023). https://doi.org/10.1134/S1070428023060015

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1134/S1070428023060015

Keywords:

Search

Navigation