Communication
The Concerted Nature of the Cyclization of Squalene Oxide to the Protosterol Cation
Prof. Dr. B. Andes Hess Jr.,
Prof. Dr. Lidia Smentek,
Corresponding Author
Prof. Dr. B. Andes Hess Jr.
Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA)
Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA)Search for more papers by this authorProf. Dr. Lidia Smentek
Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA)
Search for more papers by this authorProf. Dr. B. Andes Hess Jr.,
Prof. Dr. Lidia Smentek,
Corresponding Author
Prof. Dr. B. Andes Hess Jr.
Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA)
Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA)Search for more papers by this authorProf. Dr. Lidia Smentek
Department of Chemistry, Vanderbilt University, Nashville, TN 37235 (USA)
Search for more papers by this authorGraphical Abstract
Concerted A–C ring formation: A concerted, but highly asynchronous, pathway was identified for the formation of rings A–C in the biosynthetic conversion of squalene oxide to the prosterol cation, with ring B being formed in the required boat conformation.
Supporting Information
As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.
| Filename | Description |
|---|---|
| anie_201302886_sm_miscellaneous_information.pdf287.4 KB | miscellaneous_information |
Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.
References
- 1I. M. Heilbron, E. D. Kamm, W. M. Owens, J. Chem. Soc. 1926, 1630–1644.
- 2R. G. Langdon, K. Bloch, J. Am. Chem. Soc. 1952, 74, 1869–1870.
- 3R. B. Woodward, K. Bloch, J. Am. Chem. Soc. 1953, 75, 2023–2024.
- 4E. J. Corey, W. E. Russey, P. R. Ortiz de Montellano, J. Am. Chem. Soc. 1966, 88, 4750–4751.
- 5E. E. van Tamelen, J. D. Willett, R. B. Clayton, J. Am. Chem. Soc. 1967, 89, 3371–3373.
- 6For reviews, see:
- 6aD. U. Cane, Chem. Rev. 1990, 90, 1089–1103;
- 6bK. U. Wendt, G. E. Schulz, E. J. Corey, D. R. Liu, Angew. Chem. 2000, 112, 2930–2952;
10.1002/1521-3757(20000818)112:16<2930::AID-ANGE2930>3.0.CO;2-S Google ScholarAngew. Chem. Int. Ed. 2000, 39, 2812–2833;10.1002/1521-3773(20000818)39:16<2812::AID-ANIE2812>3.0.CO;2-# CAS PubMed Web of Science® Google Scholar
- 6cI. Abe, M. Rohmerk, G. D. Prestwich, Chem. Rev. 1993, 93, 2189–2206;
- 6dJ. D. Connolly, R. A. Hill, Nat. Prod. Rep. 2001, 18, 560–578;
- 6eR. F. Xu, G. C. Fazio, S. P. T. Matsuda, Phytochemistry 2004, 65, 261–291;
- 6fR. A. Yoder, J. N. Johnston, Chem. Rev. 2005, 105, 4730–4756;
- 6gD. W. Christianson, Chem. Rev. 2006, 106, 3412–3442;
- 6hI. Abe, Nat. Prod. Rep. 2007, 24, 1311–1331;
- 6iJ. Degenhardt, T. G. Köllner, J. Ger shenzon, Phytochemistry 2009, 70, 1621–1637;
- 6jD. J. Tantillo, Nat. Prod. Rep. 2011, 28, 1035–1053.
- 7B. A. Hess, Jr., J. Am. Chem. Soc. 2002, 124, 10286–10287.
- 8
- 8aY. J. Hong, D. J. Tantillo, Org. Lett. 2006, 8, 4601–4604;
- 8bM. W. Lodewyk, P. Gutta, D. J. Tantillo, J. Org. Chem. 2008, 73, 6570–6579;
- 8cY. J. Hong, D. J. Tantillo, J. Am. Chem. Soc. 2009, 131, 7999–8015;
- 8dY. J. Hong, D. J. Tantillo, J. Am. Chem. Soc. 2010, 132, 5375–5386.
- 9
- 9aB. A. Hess, Jr., Org. Lett. 2003, 5, 165–167;
- 9bB. A. Hess, Jr., Collect. Czech. Chem. Commun. 2003, 68, 202–210;
- 9cB. A. Hess, Jr., Eur. J. Org. Chem. 2004, 2239–2242;
- 9dB. A. Hess, Jr., L. Smentek, Mol. Phys. 2004, 102, 1201–1206.
- 10D. J. Reinert, G. Balliano, G. E. Schulz, Chem. Biol. 2004, 11, 121–126.
- 11L. Smentek, B. A. Hess, Jr., J. Am. Chem. Soc. 2010, 132, 17111–17117.
- 12
- 12aAll calculations were performed with Gaussian 09 (Revision A.02), M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, D. J. Fox, Gaussian, Inc., Wallingford CT, 2009;
- 12bGeometries were optimized without symmetry constraints using BB1K/6-31G* (M. Weitman, D. T. Major, J. Am. Chem. Soc. 2010, 132, 6349–6360; Y. Zhao, B. J. Lynch, D. G. Truhlar, J. Phys. Chem. A 2004, 108, 2715–2719; C. Lee, W. Yang, R. Parr, Phys. Rev. B 1988, 37, 785–789; P. C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213–222). All structures were characterized by frequency calculations, and reported energies include zero-point energy corrections (unscaled). Intrinsic reaction coordinate (IRC) calculations ( C. Gonzalez, H. B. Schlegel, J. Phys. Chem. 1990, 94, 5523–5527; K. Fukui, Acc. Chem. Res. 1981, 14, 363–368) were also used to verify the identity of all transition structures.
- 13The initial guess for this transition structure made use of the results of our earlier calculations on a model system of the part of squalene that contained only those carbons necessary for the A(chair)–B(boat)ring closures (see Ref. [11]). The conformation of the remaining carbons that would form the C ring was chosen to give the proper stereochemistry of the C rings in the product.
- 14BB1K/6-31G* calculations were carried out for the previous B3LYP/6-31G study of the concerted ring closure of the ABC rings in the cyclization of squalene to the hopenes (Ref. [11]), the results of which are given in the Supporting Information.
- 15D. Gao, Y.-K. Pan, K. Byun, J. Gao, J. Am. Chem. Soc. 1998, 120, 4045–4046.
- 16Our earlier calculation on this C-ring expansion/D-ring formation was carried out with B3LYP/6-31G*, which both Matsuda (S. P. T. Matsuda, W. K. Wilson, Q. Xiong, Org. Biomol. Chem. 2006, 4, 530–543) and Major ( M. Weitman, D. T. Major, J. Am. Chem. Soc. 2010, 132, 6349–6360) have noted does not give reliable energies for cyclizations of hydrocarbons. Major has found that the BB1K method on the other hand does.
- 17R. Thoma, T. Schulz-Gasch, B. D′Arcy, J. Benz, J. Aebi, H. Dehmlow, M. Hennig, M. Stihle, A. Ruf, Nature 2004, 432, 118–122.
- 18
- 18aT.-K. Wu, T.-T. Wang, C.-H. Chang, Y.-T. Liu, W.-S. Shie, Org. Lett. 2008, 10, 4959–4962;
- 18bT.-K. Wu, C.-H. Chang, Y.-T. Liu, T.-T. Wang, Chem. Rec. 2008, 8, 302–325;
- 18cT.-K. Wu, Y.-C. Chang, Y.-T. Liu, C-.H. Chang, H.-Y. Wen, W.-H. Li, W.-S. Shie, Org. Biomol. Chem. 2011, 9, 1092–1097;
- 18dB. Tian, L. Eriksson, J. Phys. Chem. B 2012, 116, 13857–13862;
- 18eG. Siedenburg, D. Jendrossek, Appl. Environ. Microbiol. 2011, 77, 3905–3915.
