Redox electron-transfer reactions: Electrochemically mediated rearrangement, mechanism, and a total synthesis of daucene

Journal of Organic Chemistry

Volumn 73, Issue 17, 2008, Pages 6807-6815

  Young, Sam Park ^a   Little, R Daniel ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINES; CHEMICAL REACTIONS; ELECTRON TRANSITIONS; OLEFINS; ORGANIC COMPOUNDS; PARAFFINS; RAW MATERIALS; REDOX REACTIONS;

CATION RADICALS; EQUILIBRIUM STATES; TOTAL SYNTHESIS;

FREE RADICAL REACTIONS;

ALKANE; ALKENE; AMINE; CARBON; DAUCENE; METHYL GROUP; PENTANE; SESQUITERPENE DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; COMPARATIVE STUDY; CYCLIC POTENTIOMETRY; ELECTROCHEMISTRY; ELECTRON TRANSPORT; ENERGY; OXIDATION; OXIDATION REDUCTION REACTION; QUANTITATIVE ANALYSIS; QUANTUM MECHANICS; STRUCTURE ANALYSIS; SUBSTITUTION REACTION; SYNTHESIS;

AMINES; BICYCLO COMPOUNDS; CATALYSIS; CYCLOPENTANES; ELECTROCHEMISTRY; ELECTRON TRANSPORT; FREE RADICALS; IMIDES; MODELS, CHEMICAL; OXIDATION-REDUCTION; SESQUITERPENES; THERMODYNAMICS;

EID: 51549121198     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo801199s     Document Type: Article

References (34)

1. (a) Park, Y. S.; Wang, S. C.; Tantillo, D. J.; Little, R. D. J. Org. Chem. 2007, 72, 4351-4357.
2. (b) Gerken, J. B.; Wang, S. C.; Preciado, A. B.; Park, Y. S.; Nishiguchi, G.; Tantillo, D. J.; Little, R. D. J. Org. Chem. 2005, 70, 4598-4608.
3. As a component in flavors and fragrances, see: Mazzoni, V.; Tomi, F.; Casanova, J. Flavour Fragr. J. 1999, 14, 268-272.
4. For previous synthetic efforts, see: (a) Pigulevskii, G. V.; Kivaleva, V. I. Doklady Akad. Nauk S.S.S.R. 1961, 141, 1382.
5. (b) Sriraman, M. C.; Nagasampagi, B. A.; Pandey, R. C.; Dev, S. Tetrahedron 1973, 29, 985-991.
6. (c) Audenaert, F.; Keukeleire, D. D.; Vandewalle, M. Tetrahedron 1987, 43, 5593-5604.
7. (d) Naegeli, P.; Kaiser, R. Tetrahedron Lett. 1972, 13, 2013-2016.
8. (e) Seto, H.; Fujimoto, Y.; Tatsuno, T.; Yoshioka, H. Synth. Commun. 1985, 15, 1217-1224.
9. (f) Mehta, G.; Krishnamurthy, N. Synth. Commun. 1985, 18, 1267-1274.
10. (g) Yamasaki, M. J. Chem. Soc., Chem. Commun 1972, 606-607.
11. (h) deBroissia, H.; Levisalles, J.; Rudler, H. Bull. Soc. Chim. Fr. 1972, 4314-4318.
12. Srikrishna, A., Kumar, P. P. Tetrahedron 2000, 56, 8189-8195.
13. 13C NMR spectrum confirmed the presence of the alkene.
14. Fraga, B. M. Nat. Prod. Rep. 1992, 9, 217-241.
15. (a) Ciminale, F.; Lopez, L.; Farinola, G. M.; Sportelli, S.; Nacci, A. Eur. J. Org. Chem. 2002, 3850-3854.
16. •+ changed to a dark yellow. An additional 20 mol % of the antimonate was needed to maintain the blue color and drive the reaction to completion.
17. A larger than customary amount of the trisarylamine was used in an effort to force the reaction to completion with the expectation of an increase in the yield. Unfortunately, this did not prove to be the case. Rather than having the desired outcome, the presence of additional mediator led to the oxidation of the product, with the formation of an unidentified byproduct as soon as the starting material was consumed.
18. We are well aware of the fact that the sequence from the rearrangement product 7 to daucene could have been conducted in a more elegant manner. We opted, instead, for an expeditious approach and to focus our attention upon gaining an understanding of the fundamental chemistry of cation radicals and mediated redox processes.
19. Shao, Y.; Molnar, L. F.; Jung, Y.; Kussmann, J.; Ochsenfeld, C.; Brown, S. T.; Gilbert, A. T. B.; Slipchenko, L. V.; Levchenko, S. V.; O'Neill, D. P.; DiStasio, R. A., Jr.; Lochan, R. C.; Wang, T.; Beran, G. J. O.; Besley, N. A.; Herbert, J. M.; Lin, C. Y.; Van Voorhis, T.; Chien, S. H.; Sodt, A.; Steele, R. P.; Rassolov, V. A.; Maslen, P. E.; Korambath, P. P.; Adamson, R. D.; Austin, B.; Baker, J.; Byrd, E. F. C.; Dachsel, H.; Doerksen, R. J.; Dreuw, A.; Dunietz, B. D.; Dutoi, A. D.; Furlani, T. R.; Gwaltney, S. R.; Heyden, A.; Hirata, S.; Hsu, C.-P.; Kedziora, G.; Khalliulin, R. Z.; Hunzinger, P.; Lee, A. M.; Lee, M. S.; Liang, W. Z.; Lotan, I.; Nair, N.; Peters, B.; Proynov, E. I.; Pieniazek, P. A.; Rhee, Y. M.; Ritchie, J.; Rosta, E.; Sherrill, C. D.; Simmonett. A. C.; Subotnik, J. E.; Woodcock, H. L., III; Zhang, W.; Bell, A. T.; Chakraborty, A. K.; Chipman, D. M.; Keil, F. J.; Warshel, A.; Hehre, W. J.; Schaefer, H. F.; Kong, J.; Krylov, A. I.; Gill, P. M. W.; Head-Gordon, M. Phys. Chem. Chem. Phys. 2006, 8, 3172.
20. Wu, X.; Davis, A. P.; Fry, A. J. Org. Lett. 2007, 9, 5633-5636.
21. (a) That the second wave in each voltammogram corresponds to the products was confirmed by overlaying the curves of products with the curves shown in Figure 2.
22. (b) Notice the broad, ill-defined nature of the voltammograms, independent of whether the benzyloxy groups was present or absent.
23. Consideration of the Nernst equation reveals how this is so. Thus, the faster the rate of the process that follows the initial redox equilibrium, the larger will be the factor that is subtracted. The consequence, of course, is to make easier the redox process being studied. For a beautiful example of these thoughts and their consequences, refer to: Moeller, K. D.; Tinao, L. V. J. Am. Chem. Soc. 1992, 114, 1033-1041.
24. (a) Kaimakliotis, C.; Fry, A. J. J. Org. Chem. 2003, 68, 9893-9898.
25. (b) Yoshida, J-I.; Maekawa, T.; Murata, T.; Matsunaga, S-i.; Ism, S. J. Am. Chem. Soc. 1990, 112, 1962-1970.
26. Foster, J. P., Weinhold, F. J. Am. Chem. Soc. 1980, 102, 7211-7218.
27. The broad, ill-defined nature of the voltammograms is reminiscent of the lack of definition that is often encountered in ultraviolet absorption spectra.
28. (a) Pigulevkii, G. V.; Kivaleva, V. I. Doklady Akad. Nauk S.S.S.R. 1961, 141, 1382.
29. (b) Sriraman, M. C.; Nagasampagi, B. A.; Pandey, R. C.; Dev, S. Tetrahedron 1973, 29, 985-991.
30. (c) Audenaert, F.; Keukeleire, D. D.; Vandewalle, M. Tetrahedron 1987, 43, 5593-5604.
31. (d) Naegeli, P.; Kaiser, R. Tetrahedron Lett. 1972, 13, 2013-2016.
32. (e) Seto, H.; Fujimoto, Y.; Tatsuno, T.; Yoshioka, H. Synth. Commun. 1985, 15, 1217-1224.
33. (f) Mehta, G.; Krishnamurthy, N. Synth. Commun. 1985, 18, 1267-1274.
34. (g) Momchilova, S.; Nikolova-Damyanova, B. J. Sep. Sci. 2003, 26, 261-270.