Axanes

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The basic substance of the axans: axan

Axans (stress on the second syllable: Ax a ne ) are a small group of spirocyclic sesquiterpenes .

properties

The eponymous substance axanane (C 15 H 26 ) has a molar mass of 206.37 g · mol −1 . While in the other group of spirocyclic sesquiterpenes, the acoranes , the five-membered ring has an isopropyl group, the axanes differ from these through the isopropyl group on the cyclohexane ring .

The functionalized derivatives exist in both enantiomers and could be isolated from both marine and terrestrial sources. The functional group is usually a hydroxyl or isonitrile group on the C-6 carbon atom.

Representatives of these natural substances are, for example, axisonitrile , axenol and its stereoisomeric gleenol . Several total syntheses have been published for these natural products today.

biosynthesis

An alternative route is used for biosynthesis , which also leads to the synthesis of the cadinenes . As an example, the shortened biosynthetic pathway starting from germacrene to the three sesquiterpenes 4-cadinene, cadinane-4 (15), 5-diene and gleenol is shown.

Axanane Biosynthesis.svg

Occurrence

Sickle fir ( Cryptomeria japonica )
Stinging juniper ( Juniperus oxycedrus )

Terpenes with an axane structure Axisonitrile were obtained from marine sponges such as Axinella cannabina , Acanthella cavernosa , Topsentia sp. and Acanthella klethra isolated. However, these compounds could also be found in various slugs ( Phyllidia ocellata , P. variosa and Phillidiopsis krempfi ). The alcohol Gleenol was prepared from the Sachalin spruce ( Picea glehnii ), the Japanese cedar ( Cryptomeria japonica ), the wood of the reamer, juniper ( Juniperus oxycedrus ) and the brown alga Taonia atomaria isolated. From the diamond greenhouse Teclea nobilis were Teclenone isolated.

Individual evidence

  1. ↑ AC Guevel, DJ Hart: Synthesis of Carbocycles via Intramolecular Conjugate Additions: Total Syntheses of Axane Sesquiterpenoids. In: The Journal of Organic Chemistry . Volume 61, Number 2, January 1996, pp. 473-479, PMID 11666963 .
  2. ↑ K. Oesterreich, D. Spitzner: Short total synthesis of the spiro [4.5] decane sesquiterpene (-) - gleenol In: Tetrahedron , Volume 74, Number 21, May 2002, pp. 4331-4334 doi : 10.1016 / S0040-4020 (02) 00336-8 .
  3. ↑ YL Kuo, M. Dhanasekaran, CK Sha: Total syntheses of (+/-) - axamide-1 and (+/-) - axisonitrile-1 via 6-Exo-dig radical cyclization. In: The Journal of organic chemistry. Volume 74, Number 5, March 2009, pp. 2033-2038, doi : 10.1021 / jo802672t . PMID 19199661 .
  4. ↑ A. Nakazaki, T. Era, S. Kobayashi: Total synthesis of (+/-) - gleenol and (+/-) - axenol via a functionalized spiro [4.5] decane. In: Chemical & pharmaceutical bulletin . Volume 55, Number 11, November 2007, pp. 1606-1609, PMID 17978520 .
  5. ^ S. DeRosa, AD Giulio, C. Iodice, N. Zavodink: S. De Rosa, A. De Giulio, C. Iodice and N. Zavodnik: Sesquiterpenes from the brown alga Taonia atomaria . In: Phytochemistry (1994), vol. 37, pp. 1327-1330.
  6. ↑ XH Yan, XZ Zhu, JL Yu, DZ Jin, YW Guo, E. Mollo, G. Cimino: 3-Oxo-axisonitrile-3, a new sesquiterpene isocyanide from the Chinese marine sponge Acanthella sp. In: Journal of Asian Natural Products Research . Volume 8, Number 6, September 2006, pp. 579-584, doi : 10.1080 / 10286020410001721096 , PMID 16931436 .
  7. ↑ B. Di Blasio, E. Fattorusso, S. Magno, L. Maylol, C. Pedone, C. Santacroce, D. Sica, Tetrahedron , 1976, 32, 473-478.
  8. ↑ Clark, RJ, Stapleton BL, Garson MJ, Tetrahedron 2000 , 56 , 3071-3076.
  9. ↑ H. Hirota, Y. Tmono, N. Fusetani Tetrahedron 1996 , 52 , 2359-2368.
  10. ^ KA Alvi, L. Tenenbaum, P. Crews, J Nat Prod . 1991 , 54 , 71-78.
  11. ↑ CK Angerhofer, JM Pezzuto J. Nat. Prod. 1992 , 55, 1787-1789.
  12. ↑ GM König, AD Wright, O. Sticher, FR Fronczek J. Nat. Prod. 1992 , 55 , 633-638.
  13. ↑ T. Okino, E. Yoshimura, H. Hirota, N. Fusetani Tetrahedron 1996 , 52 , 9947-9954.
  14. ↑ AJ Al-Rehaily, MS Ahmad, JS Mossa, I. Muhammad: New Axane and oppositane Sesquiterpenes from Teclea nobilis. In: Journal of Natural Products . Volume 65, Number 9, September 2002, pp. 1374-1376, PMID 12350171 .