Thermal isomerization of (+)-cis- and (-)-trans-pinane leading to (-)-β-citronellene and (+)-isocitronellene

Chemistry - A European Journal

Volumn 14, Issue 22, 2008, Pages 6805-6814

  Stolle, Achim ^a   Ondruschka, Bernd ^a   Bonrath, Werner ^a,b   Netscher, Thomas ^b   Findeisen, Matthias ^c   Hoffmann, Markus M ^d  

^a FRIEDRICH SCHILLER UNIVERSITY JENA   (Germany)

^b R and D Chemical Process Technology   (Switzerland)

^c UNIVERSITY OF LEIPZIG   (Germany)

^d STATE UNIVERSITY OF NEW YORK   (United States)

Author keywords

Ene reaction; NMR spectroscopy; Pericyclic reaction rearrangement terpenoids

Indexed keywords

CHEMICAL REACTIONS; ELECTRON TRANSITIONS; INDUSTRIAL CHEMICALS; IONIC LIQUIDS; ISOMERIZATION; ISOMERS; NETWORK PROTOCOLS; SENSOR NETWORKS;

CYCLIZATIONS; ENE REACTION; FINE CHEMICALS; FLOW-TYPE REACTORS; NMR SPECTROSCOPY; PERICYCLIC REACTION REARRANGEMENT TERPENOIDS; REACTION MECHANISMS; REARRANGEMENT REACTIONS; SIDE REACTIONS; SYNTHESIS OF; TERPENOIDS;

COMPLEXATION;

BETA CITRONELLENE; BETA-CITRONELLENE; ISOCITRONELLENE; PINANE; TERPENE;

ARTICLE; CHEMISTRY; MASS SPECTROMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM; SYNTHESIS; TEMPERATURE;

MAGNETIC RESONANCE SPECTROSCOPY; MASS SPECTROMETRY; MONOTERPENES; STEREOISOMERISM; TEMPERATURE; TERPENES;

EID: 53849132009     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.200800298     Document Type: Article

References (40)

1. E. P. Serebryakov, N. C. Hao, M. V. Mavrov, Pure Appl. Chem. 1990, 62, 2041-2046.
2. K. A. D. Swift, Top. Catal. 2004, 27, 143-155.
3. J. L. F. Monteiro, C. O. Veloso, Top.Catal. 2004, 27, 169-180.
4. A. Stolle, B. Ondruschka, W. Bonrath, Eur. J. Org. Chem. 2007, 2310-2317.
5. R. Rienäcker, Brennst.-Chem. 1964, 45, 20-23.
6. D. V. Banthorpe, D. Whittaker, Quart. Rev. 1966, 20, 373-387.
7. Y. R. Naves, Russ. Chem. Rev. 1968, 37, 779-788.
8. J. J. Gajewski, I. Kuchuk, C. M. Hawkins, R. Stine, Tetrahedron 2002, 58, 6943-6950.
9. V. A. Semikolenov, I. I. Illína, I. L. Simakova, Appl. Catal. A 2001, 211, 91-107.
10. A. Stolle, C. Brauns, M. Nüchter, B. Ondruschka, W. Bonrath, M. Findeisen, Eur. J. Org. Chem. 2006, 3317-3325.
11. A.M. Chibiryaev, A. Yermakova, I. V. Kozhevnikov, O. I. Sal'nikova, V. I. Anikeev, Russ. Chem. Bull. 2007, 56, 1234-1238.
12. Superscript numbers refer to the numbering of the carbon or hydrogen atoms of the desired molecules, following IUPAC rules, cf. H. Schick, K.-H. Hellwich, Angew. Chem. 2005, 117, 7985-8014.
13. J. Tanaka, T. Katagiri, K. Izawa, Bull. Chem. Soc. Jpn. 1970, 44, 130-132.
14. W. D. Huntsman, T. H. Curry, J Am. Chem. Soc 1958, 80, 2252-2254.
15. H. Strickler, G. Ohloff, E. sz. Kovats, Helv. Chim. Acta 1967, 50, 759-797.
16. V. N. Ipatieff, W. D. Huntsman, H. Pines, J. Am. Chem. Soc. 1953, 75, 6222-6225.
17. H. Pines, N. E. Hoffman, V. N. Ipatieff, J. Am. Chem. Soc 1954, 76, 4412-4416.
18. R. Rienäcker, G. Ohloff, Angew. Chem. 1961, 73, 240.
19. J.-B. Lee, C.-B. Kim, Anal. Sci. Technol. 1992, 5, 373-379; CAN: 119:117556.
20. L. Lemée, M. Ratier, J.-G. Duboudin, B. Delmond, Synth. Commun. 1995, 25, 1313-1318.
21. W. Daniewski, A. Dambska, Tluszcze, Srodki Piorace, Kosmetyki 1969, 13, 229-233; CAN: 72:100903.
22. I. Pianet, M. Dolatkhani, H. Cramail, A. Deffieux, G. Bourgeois, J. Chim. Phys. Phys.-Chim. Bio. 1995, 92, 1813-1817.
23. F. J. McQuillin, D. G. Parker, J. Chem. Soc. Perkin Trans. 1 1974, 809-815.
24. J. M. Coxon, R. P. Garland, M. P. Hartshorn, Aust. J. Chem. 1972, 25, 353-360.
25. J. H. Horner, M. Newcomb, J. Org. Chem. 2007, 72, 1609-1616.
26. H. Strickler, G. Ohloff, E. sz. Kovats, Helv. Chem. Acta 1967, 50, 759-797.
27. J. S. Chickos, H. M. Frey, J. Chem. Soc. Perkin Trans. 1 1987, 365-370.
28. W. v. E. Doering, W. R. Roth, R. Breukmann, L. Figge, H.-W. Lennartz, W.-D. Fessner, H. Prinzbach, Chem. Ber. 1988, 121, 1-9.
29. a) R. B. Woodward, R. Hoffmann, Angew. Chem. 1969, 81, 797;
30. Angew. Chem. Int. Ed. Engl. 1969, 8, 781;
31. b) R. Hoffmann, R. B. Woodward, Science 1970, 167, 825;
32. c) R. Ponec, Top. Curr. Chem. 1995, 174, 1.
33. C. F. Mayer, J. K. Crandall, J. Org. Chem. 1970, 35, 2688-2690.
34. A. Stolle, W. Bonrath, B. Ondruschka, D. Kinzel, L. González, J. Phys. Chem. A 2008, 112, 5885-5892.
35. D. Kinzel, Diploma Thesis, Jena 2008.
36. R. L. Burwell, J. Am. Chem. Soc. 1951, 73, 4461-4462.
37. W. D. Huntsman, P. C. Lang, N. L. Madison, D. A. Uhrick, J. Org. Chem. 1962, 27, 1983-1988.
38. W. D. Huntsman, V. C. Solomon, D. Eros, J. Am. Chem. Soc. 1958, 80, 5455-5458.
39. Thermal radical sources (tert-butylperoxide, ethyleneoxide) showed no tremendous effect on selectivity and the amount of polymeric products when β-citronellene (2) is isomerized in the gas-phase (cf. reference [14]). Therefore, and because of the absence of any polymerization product, a radical chain mechanism can be ruled out.
40. According to reference [13], the other transition states/intermediates are destabilized due to ecliptic arrangements of the methyl and terminal vinyl group of β-citronellene (2). which contributes to the cyclization process.