Spin trapping of 13C-labeled p-benzynes generated by masamune-bergman cyclization of bicyclic nine-membered enediynes

Angewandte Chemie - International Edition

Volumn 43, Issue 39, 2004, Pages 5249-5253

  Usuki, Toyonobu ^a   Mita, Takashi ^a   Lear, Martin J ^a   Das, Parthasarathi ^a   Yoshimura, Fumihiko ^a   Inoue, Masayuki ^a   Hirama, Masahiro ^a   Akiyama, Kimio ^a   Tero Kubota, Shozo ^a  

^a TOHOKU UNIVERSITY   (Japan)

Author keywords

Cyclization; Enediynes; Isotopic labeling; Radicals; Spin trapping

Indexed keywords

CARBON; ISOTOPES; METHANE;

CYCLIZATION; DIFFERENTIAL REACTIVITIES; ENEDYNES; SPIN TRAPPING;

BENZENE;

ANTIBIOTIC AGENT; ANTINEOPLASTIC AGENT; BENZENE DERIVATIVE; CARBON 13; METHYL GROUP; RADICAL;

ARTICLE; CHEMICAL REACTION; CYCLIZATION; ISOTOPE LABELING; REACTION ANALYSIS; SPIN TRAPPING; THERMAL ANALYSIS; THERMODYNAMICS;

EID: 6044276841     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200454133     Document Type: Article

References (58)

1. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
2. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
3. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
4. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
5. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
6. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
7. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
8. Enediyne reviews: a) H. H. Wenk, M. Winlder, W. Sander, Angew. Chem. 2003, 115, 518; Angew. Chem. Int. Ed. 2003, 42, 502; b) Z. Xi, I. H. Goldberg in Comprehensive Natural Products Chemistry, Vol. 7 (Eds.: D. H. R. Barton, K. Nakanishi), Elsevier, Dordrecht, 1999, p. 553; c) J. W. Grissom, G. U. Gunawardena, D. Klingberg, D. Huang, Tetrahedron 1996, 52, 6453; d) M. E. Maier, Synlett 1995, 13; e) A. L. Smith, K. C. Nicolaou, J. Med. Chem. 1996, 39, 2103; K. C. Nicolaou, W.-M. Dai, Angew. Chem. 1991, 103, 1453; Angew. Chem. Int. Ed. Engl. 1991, 30, 1387.
9. J.-M. A. Battigello, M. Cui, S. Roshong, B. J. Carter, Bioorg. Med. Chem. 1995, 3, 839.
10. a) J. B. Biggins, K. C. Onwuene, J. S. Thorson, Science 2003, 301, 1537;
11. b) G. B. Jones, G. Hynd, J. M. Wright, A. Purohit, G. W. Plourde II, R. S. Huber, J. E. Mathews, A. Li, M. W. Kilgore, G. J. Bubley, M. Yancisin, M. A. Brown, J. Org. Chem. 2001, 66, 3688 and references cited therein;
12. c) M. Hashimoto, M. M. Greenberg, Y. W. Kow, J.-T. Hwang, R. P. Cunningham, J. Am. Chem. Soc. 2001, 125, 3161;
13. d) N. Zein, W. Solomon, K. L. Colson, D. R. Schroeder, Biochemistry 1995, 34, 11591.
14. a) L. H. Jones, C. W. Harwig, P. Wentworth, Jr., A. Simeonov, A. D. Wentworth, S. Py, J. A. Ashley, R. A. Lerner, K. D. Janda, J. Am. Chem. Soc. 2001, 123, 3607;
15. b) G. B. Jones, P. M. Warner, J. Org. Chem. 2001, 66, 8669.
16. a) P. G. Wenthold, R. R. Squires, W. C. Lineberger, J. Am. Chem. Soc. 1998, 120, 5279;
17. b) M. J. Schottelius, P. Chen, J. Am. Chem. Soc. 1996, 118, 4896;
18. c) R. Marquardt, A. Balster, W. Sander, E. Kraka, D. Cremer, J. G. Radziszewski, Angew. Chem. 1998, 110, 1001; Angew. Chem. Int. Ed. 1998, 37, 955;
19. c) R. Marquardt, A. Balster, W. Sander, E. Kraka, D. Cremer, J. G. Radziszewski, Angew. Chem. 1998, 110, 1001; Angew. Chem. Int. Ed. 1998, 37, 955;
20. d) B. A. Hess, Eur. J. Org. Chem. 2001, 2185;
21. e) W. Sander, Acc. Chem. Res. 1999, 32, 669;
22. f) H. H. Wenk, A. Balster, W. Sander, D. A. Hrovat, W. T. Borden, Angew. Chem. 2001, 113, 2356; Angew. Chem. Int. Ed. 2001, 40, 2295.
23. f) H. H. Wenk, A. Balster, W. Sander, D. A. Hrovat, W. T. Borden, Angew. Chem. 2001, 113, 2356; Angew. Chem. Int. Ed. 2001, 40, 2295.
24. a) P. R. Schreiner, J. Am. Chem. Soc. 1998, 120, 4184;
25. b) C. J. Cramer, J. Am. Chem. Soc. 1998, 120, 6261;
26. c) F. S. Amegayibor, J. J. Nash, A. S. Lee, J. Thoen, C. J. Petzold, H. I. Kenttamaa, J. Am. Chem. Soc. 2002, 124, 12066;
27. d) C. F. Logan, P. Chen, J. Am. Chem. Soc. 1996, 118, 2113;
28. e) A. E. Clark, E. R. Davidson, J. Am. Chem. Soc. 2001, 123, 10691;
29. f) S. Koseki, Y. Fujimura, M. Hirama, J. Phys. Chem. A 1999, 103, 7672.
30. a) For our first synthesis of 1a and our report of its thermal equilibration with 2a, see: K. Iida, M. Hirama, J. Am. Chem. Soc. 1995, 117, 8875;
31. b) for direct evidence that C-1027 and kedarcidin form paramagnetic radical species within their protective carrier apoproteins, as well as the design of a supra-C-1027 kinetically stabilized by deuteration of its apoprotein, see: M. Hirama, K. Akiyama, T. Tanaka, T. Noda, K. Iida, I. Sato, R. Hanaishi, S. Fukuda-Ishisaka, M. Ishiguro, T. Otani, J. E. Leet, J. Am. Chem. Soc. 2000, 122, 720; T. Usuki, M. Inoue, M. Hirama, T. Tanaka, J. Am. Chem. Soc. 2004, 126, 3022;
32. b) for direct evidence that C-1027 and kedarcidin form paramagnetic radical species within their protective carrier apoproteins, as well as the design of a supra-C-1027 kinetically stabilized by deuteration of its apoprotein, see: M. Hirama, K. Akiyama, T. Tanaka, T. Noda, K. Iida, I. Sato, R. Hanaishi, S. Fukuda-Ishisaka, M. Ishiguro, T. Otani, J. E. Leet, J. Am. Chem. Soc. 2000, 122, 720; T. Usuki, M. Inoue, M. Hirama, T. Tanaka, J. Am. Chem. Soc. 2004, 126, 3022;
33. c) for recent evidence that the kedarcidin chromophore undergoes spontaneous cyclization and is unlikely to require initial nucleophilic activation in vivo, see: A. G. Myers, A. R. Hurd, P. C. Hogan, J. Am. Chem. Soc. 2002, 124, 4583;
34. d) for our earlier studies on enediynes, see: K. Yoshida, Y. Minami, T. Otani, Y. Tada, M. Hirama, Tetrahedron Lett. 1994, 35, 5253; T. Mita, S. Kawata, M. Hirama, Chem. Lett. 1998, 959; T. Kaneko, M. Takahashi, M. Hirama, Angew. Chem. 1999, 111, 1347; Angew. Chem. Int. Ed. 1999, 38, 1267; T. Kaneko, M. Takahashi, M. Hirama, Tetrahedron Lett. 1999, 40, 2015.
35. d) for our earlier studies on enediynes, see: K. Yoshida, Y. Minami, T. Otani, Y. Tada, M. Hirama, Tetrahedron Lett. 1994, 35, 5253; T. Mita, S. Kawata, M. Hirama, Chem. Lett. 1998, 959; T. Kaneko, M. Takahashi, M. Hirama, Angew. Chem. 1999, 111, 1347; Angew. Chem. Int. Ed. 1999, 38, 1267; T. Kaneko, M. Takahashi, M. Hirama, Tetrahedron Lett. 1999, 40, 2015.
36. d) for our earlier studies on enediynes, see: K. Yoshida, Y. Minami, T. Otani, Y. Tada, M. Hirama, Tetrahedron Lett. 1994, 35, 5253; T. Mita, S. Kawata, M. Hirama, Chem. Lett. 1998, 959; T. Kaneko, M. Takahashi, M. Hirama, Angew. Chem. 1999, 111, 1347; Angew. Chem. Int. Ed. 1999, 38, 1267; T. Kaneko, M. Takahashi, M. Hirama, Tetrahedron Lett. 1999, 40, 2015.
37. d) for our earlier studies on enediynes, see: K. Yoshida, Y. Minami, T. Otani, Y. Tada, M. Hirama, Tetrahedron Lett. 1994, 35, 5253; T. Mita, S. Kawata, M. Hirama, Chem. Lett. 1998, 959; T. Kaneko, M. Takahashi, M. Hirama, Angew. Chem. 1999, 111, 1347; Angew. Chem. Int. Ed. 1999, 38, 1267; T. Kaneko, M. Takahashi, M. Hirama, Tetrahedron Lett. 1999, 40, 2015.
38. d) for our earlier studies on enediynes, see: K. Yoshida, Y. Minami, T. Otani, Y. Tada, M. Hirama, Tetrahedron Lett. 1994, 35, 5253; T. Mita, S. Kawata, M. Hirama, Chem. Lett. 1998, 959; T. Kaneko, M. Takahashi, M. Hirama, Angew. Chem. 1999, 111, 1347; Angew. Chem. Int. Ed. 1999, 38, 1267; T. Kaneko, M. Takahashi, M. Hirama, Tetrahedron Lett. 1999, 40, 2015.
39. For thermally-activated, 10-membered cyclic enediynes and theoretical studies, see: G. B. Jones, J. M. Wright, G. Hynd, J. K. Wyatt, P. M. Warner, R. S. Huber, A. Li, M. W. Kilgore, R. P. Sticca, R. S. Pollenz, J. Org. Chem. 2002, 67, 5727 and references cited therein.
40. P. Das, T. Mita, M. J. Lear, M. Hirama, Chem. Commun. 2002, 2624.
41. For a review of the spin-trapping method, see: E. G. Janzen, Acc. Chem. Res. 1971, 4, 31.
42. a) N. Darby, C. U. Kim, J. A. Salaüm, K. W. Shelton, S. Takada, S. Masamune, Chem. Commun. 1971, 1516; S. Masamune, N. Darby, Acc. Chem. Res. 1972, 5, 272;
43. a) N. Darby, C. U. Kim, J. A. Salaüm, K. W. Shelton, S. Takada, S. Masamune, Chem. Commun. 1971, 1516; S. Masamune, N. Darby, Acc. Chem. Res. 1972, 5, 272;
44. b) R. R. Jones, R. G Bergman, J. Am. Chem. Soc. 1972, 94, 660; R. G Bergman, Acc. Chem. Res. 1973, 6, 25.
45. b) R. R. Jones, R. G Bergman, J. Am. Chem. Soc. 1972, 94, 660; R. G Bergman, Acc. Chem. Res. 1973, 6, 25.
46. a) For the different spin-trapping behaviors of MNP and DMPO in biological EPR studies on C-1027, see: T. Usuki, M. Inoue, K. Akiyama, M. Hirama, Chem. Lett. 2002, 1148;
47. b) for related spin trapping and EPR studies, see: C. Hazlewood, M. J Davies, B. C. Gilbert, J. E. Packer, J. Chem. Soc. Perkin Trans. 2 1995, 2167; W. F. Ho, B. C. Gilbert, M. J. Davies, J. Chem. Soc. Perkin Trans. 2 1997, 2525; B. C. Gilbert, S. Silvester, P. H. Walton, A. C. Whitwood, J. Chem. Soc. Perkin Trans. 2 1999, 1891.
48. b) for related spin trapping and EPR studies, see: C. Hazlewood, M. J Davies, B. C. Gilbert, J. E. Packer, J. Chem. Soc. Perkin Trans. 2 1995, 2167; W. F. Ho, B. C. Gilbert, M. J. Davies, J. Chem. Soc. Perkin Trans. 2 1997, 2525; B. C. Gilbert, S. Silvester, P. H. Walton, A. C. Whitwood, J. Chem. Soc. Perkin Trans. 2 1999, 1891.
49. b) for related spin trapping and EPR studies, see: C. Hazlewood, M. J Davies, B. C. Gilbert, J. E. Packer, J. Chem. Soc. Perkin Trans. 2 1995, 2167; W. F. Ho, B. C. Gilbert, M. J. Davies, J. Chem. Soc. Perkin Trans. 2 1997, 2525; B. C. Gilbert, S. Silvester, P. H. Walton, A. C. Whitwood, J. Chem. Soc. Perkin Trans. 2 1999, 1891.
50. 13C-labeled MNP adducts are typically clear enough to assign the position of the pre-existing free radical, which is centered on or α to the carbon-13 atom. See also refs. [16] and [18].
51. G. Chapelet-Letourneux, H. Lemaire, A. Rassat, Bull. Soc. Chim. Fr. 1965, 11, 3283.
52. H splitting caused by the ortho-C5 β-proton (see 6a, Scheme 2); b) bis-nitroxyl spin-trapped biradicals A (if present in the EPR mixtures, Figure 1) are likely to exist in a self-quenched, quinoidal state Q: S. Nakazono, S. Karasawa, N. Koga, H. Iwamura, Angew. Chem. 1998, 110, 1645; Angew. Chem. Int. Ed. 1998, 37, 1550.
53. H splitting caused by the ortho-C5 β-proton (see 6a, Scheme 2); b) bis-nitroxyl spin-trapped biradicals A (if present in the EPR mixtures, Figure 1) are likely to exist in a self-quenched, quinoidal state Q: S. Nakazono, S. Karasawa, N. Koga, H. Iwamura, Angew. Chem. 1998, 110, 1645; Angew. Chem. Int. Ed. 1998, 37, 1550.
54. 13C = 0.710 mT: S. Y. Qian, Y.-R. Chen, L. J. Deterding, Y. C. Fann, C. F. Chignell, K. B. Tomer, R. P. Mason, Biochem. J. 2002, 363, 281.
55. It is well known that the lifetimes of free radicals are highly influenced by steric factors, for example, bulky substituents surrounding phenyl radical centers: D. Griller, K. U. Ingold, Acc. Chem. Res. 1976, 9, 13; G. Brunton, D. Griller, L. R. C. Barclay, K. U. Ingold, J. Am. Chem. Soc. 1976, 98, 6803; G. Brunton, J. A. Gray, D. Griller, L. R. C. Barclay, K. U. Ingold, J. Am. Chem. Soc. 1978, 100, 4197.
56. It is well known that the lifetimes of free radicals are highly influenced by steric factors, for example, bulky substituents surrounding phenyl radical centers: D. Griller, K. U. Ingold, Acc. Chem. Res. 1976, 9, 13; G. Brunton, D. Griller, L. R. C. Barclay, K. U. Ingold, J. Am. Chem. Soc. 1976, 98, 6803; G. Brunton, J. A. Gray, D. Griller, L. R. C. Barclay, K. U. Ingold, J. Am. Chem. Soc. 1978, 100, 4197.
57. It is well known that the lifetimes of free radicals are highly influenced by steric factors, for example, bulky substituents surrounding phenyl radical centers: D. Griller, K. U. Ingold, Acc. Chem. Res. 1976, 9, 13; G. Brunton, D. Griller, L. R. C. Barclay, K. U. Ingold, J. Am. Chem. Soc. 1976, 98, 6803; G. Brunton, J. A. Gray, D. Griller, L. R. C. Barclay, K. U. Ingold, J. Am. Chem. Soc. 1978, 100, 4197.
58. P. Barker, A. L. J. Beckwith, W. R. Cherry, R. Huie, J. Chem. Soc. Perkin Trans. 2 1985, 1147.