Structural diversity from the transannular cyclizations of natural germacrone and epoxy derivatives: A theoretical-experimental study

Chemistry - A European Journal

Volumn 19, Issue 21, 2013, Pages 6598-6612

  Pérez Morales, M Carmen ^a   Catalán, Julieta V ^a   Domingo, Victoriano ^a   Jaraíz, Martín ^b   Herrador, M Mar ^a   Quílez Del Moral, José F ^a   Lõpez Pérez, José Luis ^c   Barrero, Alejandro F ^a  

^a UNIVERSITY OF GRANADA   (Spain)

^b UNIVERSITY OF VALLADOLID   (Spain)

^c UNIVERSITY OF SALAMANCA   (Spain)

Author keywords

biosynthesis; conformational analysis; density functional calculations; ring closure; terpenes

Indexed keywords

COMPUTATIONAL CALCULATIONS; CONFORMATIONAL ANALYSIS; EPOXY-DERIVATIVES; MECHANISMS OF FORMATION; RING CLOSURES; SESQUITERPENES; STRUCTURAL DIVERGENCE; STRUCTURAL DIVERSITY;

BIOSYNTHESIS; DENSITY FUNCTIONAL THEORY; TERPENES;

BIOCHEMISTRY;

EPOXIDE; GERMACRONE; LEWIS ACID; SESQUITERPENE;

ARTICLE; CHEMICAL STRUCTURE; CHEMISTRY; CYCLIZATION; SYNTHESIS; THEORETICAL MODEL;

CYCLIZATION; EPOXY COMPOUNDS; LEWIS ACIDS; MODELS, THEORETICAL; MOLECULAR STRUCTURE; SESQUITERPENES, GERMACRANE;

EID: 84877789853     PISSN: 09476539     EISSN: 15213765     Source Type: Journal    
DOI: 10.1002/chem.201300662     Document Type: Article

References (90)

1. S. L. Schreiber, Chem. Eng. News 2003, 81, 51-61.
2. W. R. J. D. Galloway, A. Isidro-Llobet, D. R. Spring, 2010, Nat. Commun. 1:80, DOI: 10.138/ncomms1081.
3. S. L. Schreiber, Science 2000, 287, 1964
4. M. D. Burke, E. M. Berger, S. L. Schreiber, Science 2003, 302, 613-618.
5. D. R. Spring, Org. Biomol. Chem. 2003, 1, 3867.
6. K. Foo, I. Usui, D. C. G. Götz, E. W. Werner, D. Holte, P. S. Baran, Angew. Chem. Int. Ed. 2012, 51, 1-6
7. G. Valot, J. García, V. Duplan, C. Serba, S. Barluenga, N. Winssinger, Angew. Chem. 2012, 124, 5487-5490.
8. D. E. Cane, in Comprehensive Natural Products Chemistry, Vol. 2 (Eds.:, D. Barton, K. Nakanishi, O. Meth-Cohn,), Pergamon Press, Oxford, 1999; pp. 155-200
9. P. M. Dewick, in Medicinal Natural Products. A Biosynthetic Approach, 2 nd ed., Wiley, Chichester, 2004, pp. 191-203
10. although cyclases that carry out transannular cyclizations on germacradiene substrates were not characterized; however, studies based on the three-dimensional structure of 5-epi-aristolochene synthase (TEAS), a sesquiterpene cyclase from tobacco that catalyzes the cyclization of farnesyl diphosphate (FPP) to 5-epi-aristolochene, predicted that the catalysis of this enzyme includes the proton donation by Y520 for the activation of germacrene A to a eudesmane cation (see:, C. M. Starks, K. Back, J. Chappell, J. P. Noel, Science 1997, 277, 1815-1820). In this sense, it was also reported that mutation of the residue Y520 in TEAS confirms the intermediacy of germacrene A in TEAS catalysis (see
11. K. A. Rising, C. M. Starks, J. P. Noel, J. Chappell, J. Am. Chem. Soc. 2000, 122, 1861-1866).
12. A remarkable characteristic of this natural product is the spatial proximity observed between C1 and C4, both in the model obtained by X-ray diffraction (2.78 Å) and in the minimum-energy conformation 1 a of the theoretical model (2.82 Å). Surprisingly, this distance is smaller than the sum of the van der Waals radii. This proximity should facilitate, in our opinion, transannular cyclizations in this molecule. For a review on germacrone occurrence and chemical reactivity, see:, A. F. Barrero, M. M. Herrador, P. Arteaga, J. Catalán, Nat. Prod. Commun. 2008, 3, 567-576.
13. I. Loayza, D. Abujder, R. Aranda, J. Jakupovic, G. Collin, H. Deslauriers, F. Jean, Phytochemistry 1995, 38, 381-389.
14. I. Ognyanov, D. Ivanov, Perfum. Essent. Oil Rec. 1958, 49, 617-623.
15. A. F. Barrero, M. M. Herrador, P. Arteaga, J. F. Arteaga, A. G. Coloma, J. Navarro, J. Burillo, unpublished results.
16. D. C. Harrowven, G. Pattenden, in Comprehensive Organic Synthesis Vol. 3 (Eds.:, B. M. Trost, I. Fleming,), Pergamon Press, Oxford, 1991, pp. 379-411
17. G. Appendino, J. Jakupovic, G. Cravotto, M. Biavatti-Weber, Tetrahedron 1997, 53, 4681-4692.
18. A. F. Barrero, M. M. Herrador, J. L. Lõpez-Pérez, J. F. Arteaga, J. Catalán, Org. Lett. 2009, 11, 4782-4785.
19. N. Sakui, M. Kuroyanagi, Y. Ishitobi, M. Sato, A. Ueno, Phytochemistry 1992, 31, 143-147.
20. M. Yoshihara, H. Shibuya, E. Kitano, K. Yanagi, I. Kitagawa, Chem. Pharm. Bull. 1984, 32, 2059-2062
21. M. Ohshiro, M. Kuroyanagi, A. Ueno, Phytochemistry 1990, 29, 2201-2205
22. J. F. Gao, J. H. Xie, Y. Iitaka, S. Inayama, Chem. Pharm. Bull. 1989, 37, 233-236.
23. M. Yoshihara, C. Yang, C. Zheng, H. Shibuya, Y. Hamamoto, N. Tanaka, I. Kitagawa, Chem. Pharm. Bull. 1986, 34, 434-437
24. D. P. Piet, R. Schrijvers, M. C. R. Franssen, A. de Groot, Tetrahedron 1995, 51, 6303-6314
25. H. Hikino, C. Konno, T. Nagashima, T. Kohama, T. Takemoto, Chem. Pharm. Bull. 1977, 25, 6-18.
26. Gaussian 09, Revision B.01, 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.
27. C. Lee, W. Yang, R. G. Parr, Phys. Rev. B 1988, 37, 785-789
28. A. D. Becke, J. Chem. Phys. 1993, 98, 1372-1377
29. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652
30. P. J. Stephens, F. J. Devlin, C. F. Chabalowski, M. J. Frisch, J. Phys. Chem. 1994, 98, 11623-11627.
31. K. Fukui, Acc. Chem. Res. 1981, 14, 363-368
32. C. Gonzalez, J. J. W. McDouall, H. B. Schlegel, J. Phys. Chem. 1990, 94, 7467-7471.
33. D. J. Tantillo, Nat. Prod. Rep. 2011, 28, 1035-1053.
34. J. K. Sutherland, Tetrahedron 1974, 30, 1651-1660
35. A. V. Marenich, R. M. Olsen, C. P. Kelly, C. J. Cramer, D. G. Truhlar, J. Chem. Theory Comput. 2007, 3, 2011-2033
36. P. Gutta, D. J. Tantillo, J. Am. Chem. Soc. 2006, 128, 6172-6179 and references therein.
37. 4 with terpenoids gave satisfactory results:, Y. J. Hong, D. J. Tantillo, J. Org. Chem. 2007, 72, 8877-8881.
38. P. M. Imamura, R. T. Nogueira, Synth. Commun. 1995, 25, 405-412.
39. A. M. Adio, C. Paul, W. A. König, H. Muhle, Phytochemistry 2003, 64, 637-644.
40. F. Bohlmann, A. Suwita, Phytochemistry 1978, 17, 567-568.
41. A. K. Banerjee, M. Laya-Mimo, Synth. Commun. 1995, 25, 1035-1044.
42. Spartan ′08. Wavefunction, Inc., Irvine, CA (full reference in the Supporting Information).
43. M. L. Jimeno, M. C. Apreda-Rojas, F. H. Cano, B. Rodríguez, Magn. Reson. Chem. 2004, 42, 474-483.
44. V. Barone, M. Cossi, J. Tomasi, J. Comput. Chem. 1998, 19, 404-417.
45. 2], see
46. A. Gansäuer, H. Bluhm, Chem. Rev. 2000, 100, 2771-2788
47. A. Gansäuer, M. Pierobon, in Radicals in Organic Synthesis 2 (Eds.:, P. Renaud, M. P. Sibi,), Wiley-VCH, Weinheim, 2001, pp. 207-220
48. A. Gansäuer, B. Rinker, in Titanium and Zirconium in Organic Synthesis (Ed.:, I. Marek,), Wiley-VCH, Weinheim 2002, pp. 435-450
49. A. F. Barrero, J. F. Quilez del Moral, E. M. Sanchez, J. F. Arteaga, Eur. J. Org. Chem. 2006, 1627-1641
50. J. Justicia, L. Álvarez de Cienfuegos, A. G. Campaña, D. Miguel, V. Jakoby, A. Gansäuer, J. M. Cuerva, Chem. Soc. Rev. 2011, 40, 3525-3537.
51. A. Fernández-Mateos, E. Martin de La Nava, G. Pascual Coca, A. Ramos, Silva, R. Rubio González, Org. Lett. 1999, 1, 607
52. A. Gansäuer, T. Lauterbach, D. Geich-Gimbel, Chem. Eur. J. 2004, 10, 4983-4990.
53. M. R. Elliot, A.-L. Dhimane, M. Malacria, J. Am. Chem. Soc. 1997, 119, 3427-3428
54. A.-L. Dhimane, C. Aïssa, M. Malacria, Angew. Chem. 2002, 114, 3418-3421
55. Angew. Chem. Int. Ed. 2002, 41, 3284-3286
56. A. Gansäuer, D. Worgull, K. Knebel, I. Huth, G. Schnakenburg, Angew. Chem. 2009, 121, 9044-9047
57. Angew. Chem. Int. Ed. 2009, 48, 8882-8885
58. A. Gansäuer, K. Knebel, C. Kube, M. van Gastel, A. Cangönül, K. Daasbjerg, T. Hangele, M. Hülsen, M. Dolg, J. Friedrich, Chem. Eur. J. 2012, 18, 2591-2599
59. J. Friedrich, K. Walczak, M. Dolg, F. Piestert, T. Lauterbach, D. Worgull, A. Gansäuer, J. Am. Chem. Soc. 2008, 130, 1788-1796.
60. Y. Kumarasamy, P. J. Cox, M. Jaspars, L. Nahar, S. D. Sarker, Tetrahedron 2003, 59, 6403-6407.
61. A. A. Ahmed, J. Jakupovic, Phytochemistry 1990, 29, 3658-3661.
62. E. Tsankova, S. Cerrini, D. Lamba, Tetrahedron 1983, 39, 3397-3403.
63. B. M. Smith, E. J. Skellam, S. J. Oxley, A. E. Graham, Org. Biomol. Chem. 2007, 5, 1979-1982.
64. R. A. Shenvi, E. J. Corey, Org. Lett. 2010, 12, 3548-3551.
65. H. Matsuda, T. Morikawa, I. Toguchida, K. Ninomiya, M. Yoshikawa, Chem. Pharm. Bull. 2001, 49, 1558-1566.
66. III-promoted cyclization of epoxide 2 only led to one lactone.
67. T. Morikawa, H. Matsuda, K. Ninomiya, M. Yoshikawa, Biol. Pharm. Bull. 2002, 25, 627-631
68. S. Takeda, E. Hosoya, Y. Iketani, H. Mihashi, (Jpn. Kokai Tokkyo Koho), JP 01233217A 19890919, 1989.
69. For the only precedent of a natural product possessing the [4+8] bicyclic system present in 38, see:, A. Lidia Pérez, M. B. A. Caballero, A. Ortega, R. Gaviño, A. Romo de Vivar, Planta Med. 1994, 60, 263-266. There are also two precedents of cyclizations of germacrene derivatives leading to this skeleton in only 5 and <1 % yield
70. J. H. Wilton, R. W. Doskotch, J. Org. Chem. 1983, 48, 4251-4256
71. J. Castañeda-Acosta, N. H. Fischer, J. Nat. Prod. 1993, 56, 90-98.
72. M. Kuroyanagi, A. Ueno, K. Koyama, S. Natori, Chem. Pharm. Bull. 1990, 38, 55-58.
73. B. A. Hess, Jr., J. Am. Chem. Soc. 2002, 124, 10286-10287
74. D. J. Tantillo, J. Phys. Org. Chem. 2008, 21, 561-570
75. D. J. Tantillo, Chem. Soc. Rev. 2010, 39, 2847-2854; also, for clarification of terminology about these processes, see
76. Y. J. Hong, R. Ponec, D. J. Tantillo, J. Phys. Chem. A 2012, 116, 8902-8909.
77. Y. J. Hong, D. J. Tantillo, J. Am. Chem. Soc. 2009, 131, 7999-8015
78. Y. J. Hong, D. J. Tantillo, Org. Biomol. Chem. 2010, 8, 4589-4600
79. Y. J. Hong, D. J. Tantillo, J. Am. Chem. Soc. 2010, 132, 5375-5386
80. Y. J. Hong, J. L. Giner, D. J. Tantillo, J. Org. Chem. 2013, 78, 935-941; and references therein.
81. T. Toyomasu, M. Tsukahara, H. Kenmoku, M. Anada, H. Nitta, J. Ohkanda, W. Mitsuhashi, T. Sassa, N. Kato, Org. Lett. 2009, 11, 3044-3047.
82. A. Bagchi, Y. Oshima, H. Hikino, Tetrahedron 1990, 46, 1523-1530.
83. M. D. Eggers, V. Sinnwell, E. Stahl-Biskup, Phytochemistry 1999, 51, 987-990.
84. I. M. Pastor, M. Yus, Curr. Org. Chem. 2012, 16, 1277-1312.
85. B. A. Hess Jr., L. Smentek, J. P. Noel, P. E. O′Maille, J. Am. Chem. Soc. 2011, 133, 12632-12641.
86. J. Godeau, S. Olivero, S. Antoniotti, E. Duñach, Org. Lett. 2011, 13, 3320-3323
87. J. R. Lacey, P. W. Anzalone, C. M. Duncan, M. J. Hackert, R. S. Mohan, Tetrahedron Lett. 2005, 46, 8507-8511.
88. W. R. J. D. Galloway, A. Bender, M. Welch, D. R. Spring, Chem. Commun. 2009, 2446-2462.
89. R. J. Spandl, A. Bender, D. R. Spring, Org. Biomol. Chem. 2008, 6, 1149-1158.
90. D. A. Horton, G. T. Bourne, M. L. Smythe, Chem. Rev. 2003, 103, 893-930.