Concerted nature of AB ring formation in the enzymatic cyclization of squalene to hopenes

Organic Letters

Volumn 6, Issue 11, 2004, Pages 1717-1720

  Hess Jr , B Andes ^a   Smentek, Lidia ^a  

^a VANDERBILT UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

DECALIN; ENZYME; HOPANOID; SQUALENE;

ARTICLE; CHEMICAL STRUCTURE; CRYSTAL STRUCTURE; CYCLIZATION; DENSITY FUNCTIONAL THEORY; RING CLOSING METATHESIS; SYNTHESIS;

CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; INTRAMOLECULAR TRANSFERASES; MODELS, MOLECULAR; MOLECULAR CONFORMATION; SQUALENE; TRITERPENES;

EID: 2942628424     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol0496125     Document Type: Article

References (17)

1. For a recent review see: Wendt, K. U.; Schulz, G. E.; Corey, E. J.; Liu, D. R. Angew. Chem., Int. Ed. 2000, 39, 2812.
2. Jenson, C.; Jorgensen, W. L. J. Am. Chem. Soc. 1997, 119, 10846.
3. Gao, D.; Pan, Y.-K.; Byun, K.; Gao, J. J. Am. Chem. Soc. 1998, 120, 4045.
4. Hess, B. A., Jr. J. Am. Chem. Soc. 2002, 125, 10268.
5. Hess, B. A., Jr. Org. Lett. 2003, 5, 165.
6. Hess, B. A., Jr. Collect. Czech. Chem. Commun. 2003, 68, 202.
7. Hess, B. A., Jr. Eur. J. Org. Chem. In press.
8. Hess, B. A., Jr. Collect. Czech. Chem. Commun. 2004, 69, 261.
9. Reinert, D. J.; Balliano, G.; Schulz, G. E. Chem. Biol. 2004, 11, 121-126.
10. 13 were employed.
11. Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
12. Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785.
13. Hariharan, P. C.; Pople, J. A. Theor. Chim. Acta 1973, 28, 213.
14. Over 500 points were necessary to reach the bicyclic product (5). In places where the pathway was very flat (small change in energy for large change in structure) the IRC often failed and frequencies had to be recomputed and the IRC continued. Many attempts were also made to find intermediates along the pathway, particularly in the flat regions. All failed.
15. A referee suggested that this surface be checked by computing single point MP2/6-31G* energies at the DFT geometries shown in Figure 3. This was done, and a plot of these data (Figure S1 in Supporting Information) was found to be very similar to the DFT plot in Figure 4.
16. Rajamani, R.; Gao. J. J. Am, Chem. Soc. 2003, 125, 12768.
17. Poralla, K. Chem Biol. 2004, 11, 14.