7-endo radical cyclizations catalyzed by titanocene(III). Straightforward synthesis of terpenoids with seven-membered carbocycles

Journal of the American Chemical Society

Volumn 127, Issue 42, 2005, Pages 14911-14921

  Justicia, José ^a   Oller López, Juan L ^a   Campaña, Araceli G ^a   Oltra, J Enrique ^a   Cuerva, Juan M ^a   Buñuel, Elena ^b   Cárdenas, Diego J ^b  

^a UNIVERSITY OF GRANADA   (Spain)

^b UNIVERSIDAD AUTÓNOMA DE MADRID   (Spain)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOLS; AROMATIC COMPOUNDS; BIOSYNTHESIS; CATALYSIS; FREE RADICALS; KETONES; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL); TITANIUM COMPOUNDS;

7-ENDO RADICAL CYCLIZATIONS; FREE RADICAL CHEMISTRY; LAUKARLAOL; TITANOCENE(III);

ORGANOMETALLICS;

BAREKOXIDE; CYCLOHEPTANE DERIVATIVE; DAUCA 4(11),8 DIENE; FREE RADICAL; GERANYLLINALYLPYROPHOSPHATE; KARAHANAENONE; LAUKARLAOL; LINALYLPYROPHOSPHATE; NEROLIDYLPYROPHOSPHATE; TERPENOID; TITANOCENE; UNCLASSIFIED DRUG; VALPARANE DITERPENOID;

ARTICLE; BIOSYNTHESIS; CARBON NUCLEAR MAGNETIC RESONANCE; CATALYST; CHEMICAL STRUCTURE; CYCLIZATION; CYCLOADDITION; DENSITY FUNCTIONAL THEORY; REACTION ANALYSIS;

CATALYSIS; CYCLIZATION; FREE RADICALS; MODELS, CHEMICAL; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; STEREOISOMERISM; TERPENES;

EID: 27244457979     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja054316o     Document Type: Article

References (109)

1. Eliel, E. L.; Wilen, S. H.; Doyle, M. P. Basic Organic Stereochemistry; Wiley-Interscience: New York, 2001.
2. Mann, J.; Davidson, R. S.; Hobbs, J. B.; Banthorpe, D. V.; Harborne, J. B. Natural products: their chemistry and biological significance; Longman Scientific & Technical: Harlow, U.K., 1994.
3. Naya, Y.; Kotake, M. Tetrahedron Lett. 1968, 9, 1645-1649.
4. (a) Warmers, U.; König, W. A. Phytochemistry 1999, 52, 99-104.
5. (b) Cool, L. G. Phytochemistry 2001. 58, 969-972.
6. (a) Kuniyoshi, M.; Marma, M. S.; Higa, T.; Bernardinelli, G.; Jefford, C. W. J. Nat. Prod. 2001, 64, 696-700.
7. (b) Kuniyoshi, M.; Marma, M. S.; Higa, T.; Bernardinelli, G.; Jefford, C. W. Chem. Commun. 2000, 1155-1156.
8. (c) Rudi, A.; Kashman, Y. J. Nat. Prod. 1992, 55, 1408-1414.
9. Cueto, M.; Jensen, P. R.; Fenical, W. Org. Lett. 2002, 4, 1583-1585.
10. For an exhaustive overview of natural terpenoids classified by skeleton type, including most of those containing seven-membered rings, see: Connolly, J. D.; Hill, R. A. Dictionary of Terpenoids; Chapman & Hall: London, 1991.
11. For reviews, see: (a) Yet, L. Chem. Rev. 2000, 100, 2963-3007.
12. (b) Hoshomi, A.; Tominaga, Y. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Paquette, L. A., Eds.; Pergamon Press: Oxford, U.K., 1991; Vol. 5, pp 593-615.
13. Hoffmann, H. M. R. Angew. Chem., Int. Ed. Engl. 1984, 23, 1-19.
14. For selected recent reports: (d) Prié, G.; Prévost, N.; Twin, H.; Fernandes, S. A.; Hayes, J.; Shipman, M. Angew. Chem., Int. Ed. 2004, 43, 6517-6519.
15. (e) Dzwiniel, T. L.; Stryker, J. M. J. Am. Chem. Soc. 2004, 126, 9184-9185.
16. (f) Barluenga, J.; Alonso, J.; Panamas, F. J.; Borge, J.; Garcia-Granda, S. Angew. Chem., Int. Ed. 2004, 43, 5510-5513.
17. (g) López, F.; Castedo, L.; Mascareñas, J. L. Chem.-Eur. J. 2002, 8, 884-899.
18. (h) Barluenga, J.; Alonso, J.; Rodriguez, F.; Panamas, F. Angew. Chem., Int. Ed. 2000, 39, 2460-2462.
19. (i) Wender, P. A.; Glorius, F.; Husfeld, C. O.; Langkopf, E.; Love, J. A. J. Am. Chem. Soc. 1999, 121, 5348-5349.
20. For synthesis of diterpenoids with a seven-membered carbocycle by ring closing metathesis, see: (j) Pfeiffer, M. W. B.; Philips, A. J. J. Am. Chem. Soc. 2005, 127, 5334-5335.
21. (k) Nakashima, K.; Inoue, K.; Sono, M.; Tori, M. J. Org. Chem. 2002, 67, 6034-6040.
22. For a review about the Perkin ring-closure reaction, see: (a) Byrne, L. A.; Gilheany, D. G. Synlett 2004, 933-943.
23. For a review on unusual radical cyclizations, including 7-endo, see: (b) Srikrishna, A. In Radicals in Organic Synthesis; Renaud, P.. Sibi, M. P., Eds.; Wiley-VCH: Weinheim, Germany, 2001; Vol. 2, pp 151-187.
24. There are only a few reports dealing with the application of simple or cascade cyclizations for the synthesis of terpenoids containing seven-membered carbocycles. For a seminal work on the synthesis of serratenediol via cationic 7-endo cyclization, see: (c) Prestwich, G. D.; Labovitz, J. N. J. Am. Chem. Soc. 1974, 96, 7103-7105.
25. For an improved synthesis of serratenediol, see: (d) Zhang, J.; Corey, E. J. Org. Lett. 2001, 3, 3215-3216.
26. For the synthesis of two sesquiterpene guaianolides via tandem S-exo/7-endo radical cyclization, see: (e) Lee, E.; Lim, J. W.; Yoon, C. H.; Sung, Y.; Kim, Y. K.; Yun, M.; Kim, S. J. Am. Chem. Soc. 1997, 119, 8391-8392.
27. RajanBabu, T. V.; Nugent, W. A. J. Am. Chem. Soc. 1994, 116, 986-997.
28. For recent reviews covering this subject, see: (a) Gansäuer, A.; Lauterbach, T.; Narayan, S. Angew. Chem., Int. Ed. 2003, 42, 5556-5573.
29. (b) Gansauer, A.: Rinker, B. In Titanium and Zirconium in Organic Synthesis: Marek, I., Ed.; Wiley-VCH: Weinheim, Germany. 2002; pp 435-450.
30. (c) Gansäuer, A.; Narayan, S. Adv. Synth. Catal. 2002, 344, 465-475.
31. (d) Gansäuer, A.; Rinker, B. Tetrahedron 2002, 58, 7017-7026.
32. (e) Gansäuer, A.; Pierobon, M. In Radicals in Organic Synthesis; Renaud, P., Sibi, M. P., Eds.; Wiley-VCH: Weinheim, Germany. 2001; Vol. 2, pp 207-220
33. (f) Gansäuer, A.; Bluhm, H. Chem. Rev. 2000, 100, 2771-2788.
34. Enemærke, R. J.; Larsen, J.; Skrydstrup, T.; Daasbjerg, K. J. Am. Chem. Soc. 2004, 126, 7853-7864.
35. (a) Gansäuer, A.; Bluhm, H.; Pierobon, M. J. Am. Chem. Soc. 1998, 120, 12849-12859.
36. (h) Gansäuer, A.; Pierobon, M.; Bluhm, H. Angew. Chem., Int. Ed. 1998, 37, 101-103.
37. (c) Gansäuer, A.; Bluhm, H. Chem. Commun. 1998, 2143-2144.
38. Barrera, A. F.; Rosales, A.; Cuerva, J. M.; Oltra, J. E. Org. Lett. 2003, 5, 1935-1938.
39. Justicia, J.; Rosales, A.; Buñuel, E.; Oller-López, J. L.; Valdivia, M.; Haidour, A.; Oltra, J. E.; Barrero, A. F.; Cardenas, D. J.; Cuerva, J. M. Chem.-Eur. J. 2004, 10, 1778-1788.
40. (a) Bailey, W. F.; Longstaff, S. C. Org. Lett. 2001, 3, 2217-2219.
41. (b) Curran, D. P.; Porter, N. A.; Giese, B. Stereochemistry of Radical Reactions; VCH: Weinheim, Germany, 1996; pp 77-82.
42. Crich, D.; Fortt, S. M. Tetrahedron 1989, 45, 6581-6589.
43. Barrera, A. F.; Cuerva, J. M.; Herrador, M. M.; Valdivia, M. V. J. Org. Chem. 2001, 66, 4074-4078.
44. There is theoretical and experimental evidence to suggest that free-radical cyclizations take place in a stepwise manner via discrete carbon-centered radicals; see the corresponding discussion in ref 15.
45. Even the lowest yield of 39% obtained in the preparation of 20 from 12 can be regarded as satisfactory if we bear in mind that in just one step the reaction selectively provided a product containing three fused (trans/anti/trans) six-/six-/seven-membered rings, an endocyclic double bond, and five stereogenic centers, among 96 potential regio- and stereoisomers.
46. Wang, D.; Chan, T. H. Chem. Commun. 1984, 1273.
47. Widdrol, a unique sesquiterpenoid found in plants of the genus Widdringtonia, has the same carbon skeleton as 18, see: Uyehara, T.; Yamada, J.; Furuta, T.; Kato, T.; Yamamoto, Y. Tetrahedron 1987, 43, 5605-5620 and references therein.
48. Beckwith, A. L. J.; Moad, G. Chem. Commun. 1974, 472-473.
49. Hanessian, S.; Dhanoa, D. S.; Beaulieu, P. L. Can. J. Chem. 1987, 65, 1859-1866.
50. For conformational analysis of seven-membered rings, see: Eliel, E. L.; Wilen, S. H.; Doyle, M. P. Basic Organic Stereochemistry; Wiley-Interscience: New York, 2001; pp 485-487.
51. Hegedus, L. S. Transition Metals in the Synthesis of Complex Organic Molecules; University Science Books: Sausalito, CA, 1999; pp 2-4.
52. IV complexes (such as 27) toward alkenes (such as 28) is a relatively fast process, as we had previously suggested (cf., ref 14).
53. With some exceptions, such as those derived from stable nitroxyl radicals, Ti-O bonds are generally quite strong. For relevant discussions on this subject, see: (a) Huang, K.-W.; Han, J. H.; Cole, A. P.; Musgrave, C. B.; Waymouth, R. M. J. Am. Chem. Soc. 2005, 127, 3807-3816.
54. (b) Gansäuer, A.; Rinker, B.; Ndene-Schiffer, N.; Pierobon, M.; Grimme, S.; Gerenkamp, M.; Mück-Lichtenfeld, C. Eur. J. Org. Chem. 2004, 2337-2351.
55. (c) Gansäuer, A.; Rinker, B.; Pierobon, M.; Grimme, S.; Gerenkamp, M.; Mück-Lichtenfeld, C. Angew. Chem., Int. Ed. 2003, 42, 3687-3690.
56. (d) Huang, K.-W.; Waymouth, R. M. J. Am. Chem. Soc. 2002, 124, 8200-8201.
57. (e) Calhorda, M. J.; Carrondo, M. A. A. F. C. T.; Dias, A. R.; Domingos, A. M. T. S.; Simoes, J. A. M.; Teixeira, C. Organometallics 1986, 5, 660-667.
58. The stereochemistry and nonconcerted character of 6-endo-trig cyclizations leading to intermediate radicals closely related to 33, 34, 41, and 42 have been discussed elsewhere; see ref 15.
59. For a recent theoretical and experimental study of titanocene-catalyzed 3-exo cyclizations, see: Friedrich, J.; Dolg, M.; Gansäuer, A.; Geich-Gimbel, D.; Lauterbach, T. J. Am. Chem. Soc. 2005, 127, 7071-7077.
60. Although IRC studies afforded different conformers, they all can be easily interconverted. For the sake of simplicity, we have only depicted the energy of the most stable conformer. Full details can be found in the Supporting Information.
61. (a) Clayden, J.; Greeves, N.; Warren, S.; Wothers, P. Organic Chemistry; Oxford University Press: Oxford, 2001; pp 1140-1144.
62. (b) Baldwin, J. E.; Lusch, M. J. Tetrahedron 1982, 38, 2939-2947.
63. (c) Baldwin, J. E. Chem. Commun. 1976, 734-736.
64. (d) Baldwin, J. E.; Cutting, J.; Dupont, W.; Kruse, L.; Silberman, L.; Thomas, R. C. Chem. Commun. 1976, 736-738.
65. Imamura, K.; Yoshikawa, E.; Gevorsyan, V.; Yamamoto, Y. J. Am. Chem. Soc. 1998, 120, 5339-5340.
66. It should be noted that when epoxyalkynes 55 and 56 were treated with stoichiometric quantities of titanocene(III), no seven-membered ring products were detected. These results, probably due to an increased premature trapping of intermediate radicals by the high concentration of titanocene species, reinforce the synthetic value of the catalytic procedure.
67. Justicia, J.; Oltra, J. E.; Cuerva, J. M. J. Org. Chem., in press.
68. Kametani, T.; Kurobe, H.; Nemoto, H. J. Chem. Soc., Perkin Trans. 1 1981, 756-760.
69. (a) Barrero, A. F.; Alvarez-Manzaneda, E. J.; Palomino, P. L. Tetrahedron 1994, 50, 13239-13250.
70. (b) Uneyama, K.; Date, T.; Torii, S. J. Org. Chem. 1985, 50, 3160-3163.
71. See, for example, the discussion concerning the relative stereochemistry of dauca-7,11-diene: (a) Cassidy, M. P.; Ghisalberti, E. L. J. Nat. Prod. 1993, 56, 1190-1193.
72. (b) Bohlmann, F.; Zdero, C. Photochemistry 1982, 21, 2263-2267.
73. (a) Harayama, T.; Shinkai, Y.; Hashimoto, Y.; Fukushi, H.; Inubushi, Y. Tetrahedron Lett. 1983, 24, 5241-5244.
74. (b) Biellmann, J. F.; Ourisson, G. Bull. Soc. Chim. Fr. 1962, 331-336.
75. Urones, J. G.; Marcos, I. S.; Basabe, P.; Alonso, C. A.; Diez, D.; Garrido, N. M.; Oliva, I. M.; Rodilla, J. S.; Slawin, A. M. Z.; Williams, D. J. Tetrahedron Lett. 1990, 31, 4501-4504.
76. Urones, J. G.; Marcos, I. S.; Basabe, P.; Alonso, C.; Oliva, I. M.; Garrido, N. M.; Martin, D. D.; Lithgow, A. M. Tetrahedron 1993, 49, 4051-4062.
77. (a) Salomon, C. E.; Magarvey, N. A.; Sherman, D. V. Nat. Prod. Rep. 2004, 21, 105-121.
78. (b) Blunt, J. W.; Copp, B. R.; Munro, M. H. G.; Northcote, P. T.; Prinsep, M. R. Nat. Prod. Rep. 2004, 21, 1-49 and previous issues in this series.
79. Su, J. Y.; Zhong, Y. L.; Zeng, L. M.; Wu, H. M.; Ma, K. Photochemistry 1995, 40, 195-197.
80. Barekoxide was isolated from the sponge Chelonaplysilla erecta, the extract of which showed antitumoral activity (cf., ref 5c).
81. Yee, N. K. N.; Coates, R. M. J. Org. Chem. 1992, 57, 4598-4608.
82. The interatomic distance between H-14 and H-17 of 80 is 2.757 A in the minimized energy conformation shown in Figure 3 (CS ChemBats3D Pro, MOPAC).
83. 43 are given for comparison as Supporting Information.
84. 25 terpenoids, see: Dewick, P. M. Nat. Prod. Rep. 2002: 19, 181-222 and previous issues in this series.
85. For excellent reviews on this subject, see: (a) Hohino, T.; Sato, T. Chem. Commun. 2002, 291-301.
86. (b) Wendt, K. U.; Schulz, G. E.; Corey, E. J.; Liu, D. R. Angew. Chem., Int. Ed. 2000, 39, 2812-2833.
87. Abe, I.; Rohmer, M.; Prestwich, G. D. Chem. Rev. 1993, 93, 2189-2206.
88. For more recent reports, see: (d) Nishizawa, M.; Yadav, A.; Iwamoto, Y.; Imagawa, H. Tetrahedron 2004, 60, 9223-9234.
89. (e) Hess, B. A., Jr. Org. Len. 2003, 5, 165-167.
90. (f) Hess, B. A., Jr. J. Am. Chem. Soc. 2002, 124, 10286-10287.
91. Ghisalberti, E. L. Phytochemistiy 1994, 37, 597-623.
92. (a) Uyanic, M.; Ishibashi, H.; Ishihara, K.; Yamamoto, H. Org. Lett 2005, 7, 1601-1604.
93. (b) Khomenko, T. M.; Tatarova, L. E.; Korchagina, D. V.; Barkhash, V. A. Russ. J. Org. Chem. 2002, 38, 498-506.
94. (c) Polovinca, M. P.; Korchagina, D. V.; Gatilov, Y. V.; Bagrianskaya, I. Y.; Barkhash, V. A.; Shcherbukhin, V. V.; Zefirov, N. S.; Perutskii, V. B.; Ungur, N. D.; Vlad, P. F. J. Org. Chem. 1994, 59, 1509-1517.
95. (d) Kametani, T.; Fukumoto, K.; Kurobe, H.; Nemoto, H. Tetrahedron Lett. 1981, 22, 3653-3656.
96. We propose the name "barekane" for the diterpenoid skeleton shared by 3. 74, and 81.
97. Carey, F. A.; Sundberg, R. J. Advanced Organic Chemistry. 3rd ed.; Plenum Press: New York, 1990; Part A, pp 695-701.
98. Carter-Franklin, J. N.; Butler, A. J. Am. Chem. Soc. 2004, 126, 15060-15066.
99. Frisch, M. J.; et al. Gaussian 03, revision B.03; Gaussian, Inc.: Pittsburgh, PA, 2003.
100. (a) Becke, A. D. Phys. Rev. A 1988, 38, 3098-3100.
101. (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B 1988, 37, 785-789.
102. Reed, A. E.; Cuntiss, L. A.; Weinhold, F. Chem. Rev. 1988, 88, 899-926.
103. Rodriguez, J.; Dulcore, J. P. J. Org. Chem. 1991, 56, 469-471.
104. Cernigliaro, C. J.; Kocienski, P. J. J. Org. Chem. 1977, 42, 3622-3624
105. Miyase, T.; Ueno, A.; Takizawa, N.; Kobayashi, H.; Karasawa, H. Chem. Pharm. Bull. 1987, 35, 1109-11017.
106. Anjum, S.; Marco-Contellés, J. Tetrahedron 2005, 61, 4793-4803.
107. Fürstner, A.; Hammen, P. Chem. Commun. 2004, 2546-2547. See also ref 60.
108. Torii, S.; Uneyama, K.; Tanaka, H.; Yamanaka, T.; Yasuda, T.; Ono, M.; Kohmoto, Y. J. Org. Chem. 1981, 46, 3312-3315.
109. In some experiments, acidic quenching was enough to promote the desilylation reaction.