Chasing molecules that were never there: Misassigned natural products and the role of chemical synthesis in modern structure elucidation

Angewandte Chemie - International Edition

Volumn 44, Issue 7, 2005, Pages 1012-1044

  Nicolaou, K C ^a   Snyder, Scott A ^a,b  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Azaspiracid 1; Diazonamide A; Natural products; Revised structures; Total synthesis

Indexed keywords

COMPLEX MOLECULES; MOLECULAR PUZZLES; NATURAL PRODUCTS;

DEGRADATION; MASS SPECTROMETRY; MOLECULAR STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; X RAY CRYSTALLOGRAPHY;

SYNTHESIS (CHEMICAL);

AZASPIRACID; DIAZONAMIDE A; NATURAL PRODUCT; UNCLASSIFIED DRUG;

CHEMICAL REACTION KINETICS; CHEMICAL STRUCTURE; DEGRADATION KINETICS; HISTORY OF MEDICINE; MOLECULAR DYNAMICS; MOLECULAR MODEL; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OPTICAL RESOLUTION; QUANTITATIVE ANALYSIS; REACTION ANALYSIS; REVIEW; SPECTROSCOPY; STRUCTURE ANALYSIS; SYNTHESIS; TASK PERFORMANCE; X RAY CRYSTALLOGRAPHY;

BIOLOGICAL PRODUCTS; CRYSTALLOGRAPHY, X-RAY; HETEROCYCLIC COMPOUNDS WITH 4 OR MORE RINGS; HISTORY, 20TH CENTURY; HISTORY, 21ST CENTURY; HUMANS; MAGNETIC RESONANCE SPECTROSCOPY; MARINE TOXINS; MOLECULAR STRUCTURE; OXAZOLES; PHARMACOGNOSY; PLANT EXTRACTS; SPIRO COMPOUNDS;

EID: 15444378803     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200460864     Document Type: Review

References (394)

1. To explore these assignments further, see the Nobel Prize website; http://www.nobel.se/chemistry.
2. J. D. Bernal, Nature 1932, 129, 721.
3. a) P. Rabe, Ber. Dtsch. Chem. Ges. 1908, 41, 62;
4. b) P. Rabe, E. Ackerman, W. Schneider, Ber. Dtsch. Chem. Ges. 1907, 40, 3655;
5. for the first total synthesis of quinine, see: c) R. B. Woodward, W. E. Doering, J. Am. Chem. Soc. 1944, 66, 849;
6. d) R. B. Woodward, W. E. Doering, J. Am. Chem. Soc. 1945, 67, 860-874.
7. H. Fischer, K. Zeile, Justus Liebigs Ann. Chem. 1929, 468, 98.
8. a) L. H. Briggs, H. T. Openshaw, R. Robinson, J. Chem. Soc. 1946, 903-908;
9. b) R. Robinson, Experientia 1946, 2, 28;
10. for the first total synthesis of strychnine, see: c) R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger, H. U. Daeniker, K. Schenker, J. Am. Chem. Soc. 1954, 76, 4749-4751;
11. d) R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger, H. U. Daeniker, K. Schenker, Tetrahedron 1963, 19, 247-288;
12. see also: e) Robert Burns Woodward: Artist and Architect in the World of Molecules (Eds.: O. T. Benfey, P. J. T. Morris), Chemical Heritage Foundation, Philadelphia, 2001, p. 470.
13. W. von E. Doering in H. Hopf, Classics in Hydrocarbon Chemistry, Wiley-VCH, Weinheim, 2000, p. 547.
14. G. Büchi, R. E. Erickson, N. Wakabayashi, J. Am. Chem. Soc. 1961, 83, 927-938.
15. G. Büchi, W. D. MacLeod, J. Am. Chem. Soc. 1962, 84, 3205-3206.
16. a) M. Dobler, J. D. Dunitz, B. Gubler, H. P. Weber, G. Büchi, O. J. Padilla, Proc. Chem. Soc. London 1963, 383;
17. b) G. Büchi, W. D. MacLeod, O. J. Padilla, J. Am. Chem. Soc. 1964, 86, 4438-4444.
18. 4NCO. When he took a bottle of what he thought was silver isocyanate (actually silver cyanate), added ammonium chloride, and heated, urea resulted, an outcome that he did not intend, but one which was fortuitous nonetheless. For an interesting discussion on Wöhler's synthesis of urea, see: P. S. Cohen, S. M. Cohen, J. Chem. Educ. 1996, 73, 883-886.
19. a) K. Nakanishi in Comprehensive Natural Products Chemistry, Vol. 1 (Eds.: D. H. R. Barton, K. Nakanishi, O. Meth-Cohn), Elsevier, Amsterdam, 1999, pp. xxiii-xl;
20. b) C. Djerassi, Pure Appl. Chem. 1975, 41, 113-144;
21. for an interesting recent account on two misassignments in inorganic chemistry, see: c) J. A. Labinger, S. J. Weininger, Angew. Chem. 2004, 116, 2664-2672; Angew. Chem. Int. Ed. 2004, 43, 2612-2619.
22. for an interesting recent account on two misassignments in inorganic chemistry, see: c) J. A. Labinger, S. J. Weininger, Angew. Chem. 2004, 116, 2664-2672; Angew. Chem. Int. Ed. 2004, 43, 2612-2619.
23. J. C. Sheehan, The Enchanted Ring: The Untold Story of Penicillin, MIT Press, Cambridge, 1984, p. 224.
24. C. Djerassi, Steroids Made It Possible (Ed.: J. I. Seeman), American Chemical Society, Washington, DC, 1990, p. 205 (Profiles, Pathways and Dreams Series).
25. K. Nakanishi, A Wandering Natural Products Chemist (Ed.: J. I. Seeman), American Chemical Society, Washington, D.C., 1991, p. 230 (Profiles, Pathways and Dreams Series). The quote is on page 87. For a further insightful analysis of the state of the art of total synthesis in 1974, see: A. Eschenmoser, Naturwissenschaften 1974, 61, 513-525.
26. K. Nakanishi, A Wandering Natural Products Chemist (Ed.: J. I. Seeman), American Chemical Society, Washington, D.C., 1991, p. 230 (Profiles, Pathways and Dreams Series). The quote is on page 87. For a further insightful analysis of the state of the art of total synthesis in 1974, see: A. Eschenmoser, Naturwissenschaften 1974, 61, 513-525.
27. a) L. L. Klein, W. W. McWhorter, S. S. Ko, K.-P. Pfaff, Y. Kishi, D. Uemura, Y. Hirata, J. Am. Chem. Soc. 1982, 104, 7362-7364;
28. b) S. S. Ko, J. M. Finan, M. Yonaga, Y. Kishi, D. Uemura, Y. Hirata, J. Am. Chem. Soc. 1982, 104, 7364-7367;
29. c) H. Fujioka, W. J. Christ, J. K. Cha, J. Leder, Y. Kishi, D. Uemura, Y. Hirata, J. Am. Chem. Soc. 1982, 104, 7367-7369;
30. d) J. K. Cha, W. J. Christ, J. M. Finan, H. Fujioka, Y. Kishi, L. L. Klein, S. S. Ko, J. Leder, W. W. McWhorter, K.-P. Pfaff, M. Yonaga, D. Uemura, Y. Hirata, J. Am. Chem. Soc. 1982, 104, 7369-7371; for a detailed account of this synthesis, see: K. C. Nicolaou, E. J. Sorensen, Classics in Total Synthesis: Targets, Strategies, Methods, VCH, Weinheim, 1996, chap. 36, p. 798.
31. d) J. K. Cha, W. J. Christ, J. M. Finan, H. Fujioka, Y. Kishi, L. L. Klein, S. S. Ko, J. Leder, W. W. McWhorter, K.-P. Pfaff, M. Yonaga, D. Uemura, Y. Hirata, J. Am. Chem. Soc. 1982, 104, 7369-7371; for a detailed account of this synthesis, see: K. C. Nicolaou, E. J. Sorensen, Classics in Total Synthesis: Targets, Strategies, Methods, VCH, Weinheim, 1996, chap. 36, p. 798.
32. M. Ishibashi, N. Yamaguchi, T. Sasaki, J. Kobayashi, J. Chem. Soc. Chem. Commun. 1994, 1455-1456.
33. Our SciFinder search terms included: revised structure, structural reassignment, misassigned structure, incorrect structure, putative structure, tentative structure, and structural revision. Interestingly, each of these searches produced quite a different set of results, and well over 1000 hits were obtained overall for the period of January 1990 to March 2004.
34. R. Suemitsu, K. Ohnishi, M. Horiuchi, A. Kitaguchi, K. Odamura, Phytochemistry 1992, 31, 2325-2326.
35. M. Horiuchi, T. Maoka, N. Iwase, K. Ohnishi, J. Nat. Prod. 2002, 65, 1204-1205.
36. I. Cornella, T. R. Kelly, J. Org. Chem. 2004, 69, 2191-2193.
37. A. S. Ratnayake, W Y. Yoshida, S. L. Mooberry, T. K. Hemscheidt, J. Org. Chem. 2001, 66, 8717-8721.
38. J. A. May, R. K. Zeidan, B. M. Stoltz, Tetrahedron Lett. 2003, 44, 1203-1205. Nomofungin is identical to the natural product communesin B, which had been isolated and characterized almost a decade earlier: A. Numata, C. Takahashi, Y. Ito, T. Takada, K. Kawai, Y. Usami, E. Matsumura, M. Imachi, T. Ito, T. Hasegawa, Tetrahedron Lett. 1993, 34, 2355-2358.
39. J. A. May, R. K. Zeidan, B. M. Stoltz, Tetrahedron Lett. 2003, 44, 1203-1205. Nomofungin is identical to the natural product communesin B, which had been isolated and characterized almost a decade earlier: A. Numata, C. Takahashi, Y. Ito, T. Takada, K. Kawai, Y. Usami, E. Matsumura, M. Imachi, T. Ito, T. Hasegawa, Tetrahedron Lett. 1993, 34, 2355-2358.
40. I. H. Hardt, P. R. Jensen, W. Fenical, Tetrahedron Lett. 2000, 41, 2073-2076.
41. J. A. Kalaitzis, Y. Hamano, G. Nilsen, B. S. Moore, Org. Lett. 2003, 5, 4449-4452.
42. P. A. Horton, F. E. Koehn, R. E. Longley, O. J. McConnell, J. Am. Chem. Soc. 1994, 116, 6015-6016.
43. a) E. Lee, H. Y. Song, J. W. Kang, D.-S. Kim, C.-K. Jung, J. M. Joo, J. Am. Chem. Soc. 2002, 124, 384-385;
44. b) E. Lee, H. Y. Song, J. M. Joo, J. W. Kang, D. S. Kim, C. K. Jung, C. Y. Hong, S. Jeong, K. Jeon, Bioorg. Med. Chem. Lett. 2002, 12, 3519-3520;
45. c) H. Y. Song, J. M. Joo, J. W. Kang, D.-S. Kim, C.-K. Jung, H. S. Kwak, J. H. Park, E. Lee, C. Y. Hong, S. Jeong, K. Jeon, J. H. Park, J. Org. Chem. 2003, 68, 8080-8087. In this reassignment not only was an error found in the proposed structure, but the sign of the optical rotation reported for the natural product was also incorrect.
46. A. Randazzo, G. Bifulco, C. Giannini, M. Bucci, C. Debitus, G. Cirino, L. Gomez-Paloma, J. Am. Chem. Soc. 2001, 123, 10870-10876.
47. C. Della Monico, A. Randazzo, G. Bifulco, P. Cimino, M. Aquino, I. Izzo, F. De Riccardis, L. Gomez-Paloma, Tetrahedron Lett. 2002, 43, 5707-5710.
48. P. Sharma, M. Alam, J. Chem. Soc. Perkin Trans. 1 1988, 2537-2540.
49. a) L. A. Paquette, O. M. Moradei, P. Bernardelli, T. Lange, Org. Lett. 2000, 2, 1875-1878;
50. b) D. Friedrich, R. W. Doskotch, L. A. Paquette, Org. Lett. 2000, 2, 1879-1882;
51. for the full account of this reassignment, see: c) D. Friedrich, L. A. Paquette, J. Nat. Prod. 2002, 65, 126-130;
52. for another synthesis of the originally assigned structure of sclerophytin A, see: d) L. E. Overman, L. D. Pennington, Org. Lett. 2000, 2, 2683-2686.
53. a) F. Gallou, D. W. C. MacMillan, L. E. Overman, L. A. Paquette, L. D. Pennington, J. Yang, Org. Lett. 2001, 3, 135-137;
54. for the full account of these total syntheses, see: b) P. Bernardelli, O. M. Moradei, D. Friedrich, J. Yang, F. Gallou, B. P. Dyck, R. W. Doskotch, T. Lange, L. A. Paquette, J. Am. Chem. Soc. 2001, 123, 9021-9032;
55. c) D. W. C. MacMillan, L. E. Overman, L. D. Pennington, J. Am. Chem. Soc. 2001, 123, 9033-9044;
56. for a personal account of one of these research programs, see: d) L. A. Paquette, Chem. Rec. 2001, 1, 311-320;
57. e) L. A. Paquette, Chemtracts 2002, 15, 345-366.
58. A. D. Patil, A. J. Freyer, P. B. Taylor, B. Carté, G. Zuber, R. K. Johnson, D. J. Faulkner, J. Org. Chem. 1997, 62, 1814-1819.
59. a) F. Cohen, L. E. Overman, J. Am. Chem. Soc. 2001, 123, 10782-10783.
60. Earlier work by other groups had revised the stereostructure of the left-hand guanidine portion of batzelladine F, but the carbon framework was not corrected: b) G. P. Black, P. J. Murphy, A. J. Thornhill, N. D. A. Walshe, C. Zanetti, Tetrahedron 1999, 55, 6547-6554;
61. c) B. B. Snider, M. V. Busuyek, J. Nat. Prod. 1999, 62, 1707-1711;
62. d) K. Nagasawa, H. Koshino, T. Nakata, Tetrahedron Lett. 2001, 42, 4155-4158.
63. S. Carmely, Y. Kashman, Tetrahedron Lett. 1985, 26, 511-514.
64. a) M. Kobayashi, J. Tanaka, T. Katori, M. Matsuura, I. Kitagawa, Tetrahedron Lett. 1989, 30, 2963-2966;
65. b) I. Kitagawa, M. Kobayashi, T. Katori, M. Yamashita, J. Tanaka, M. Doi, T. Ishida, J. Am. Chem. Soc. 1990, 112, 3710-3712;
66. c) M. Kobayashi, J. Tanaka, T. Katori, M. Matsuura, M. Yamashita, I. Kitagawa, Chem. Pharm. Bull. 1990, 38, 2409-2418;
67. d) M. Kobayashi, J. Tanaka, T. Katori, I. Kitagawa, Chem. Pharm. Bull. 1990, 38, 2960-2966;
68. e) M. Doi, T. Ishida, M. Kobayashi, I. Kitagawa, J. Org. Chem. 1991, 56, 3629-3632.
69. a) I. Paterson, J. D. Smith, R. A. Ward, J. G. Cumming, J. Am. Chem. Soc. 1994, 116, 2615-2616;
70. b) I. Paterson, K.-S. Yeung, R. A. Ward, J. G. Gumming, J. D. Smith, J. Am. Chem. Soc. 1994, 116, 9391-9392;
71. for the full account of this total synthesis, see: c) I. Paterson, J. G. Cumming, R. A. Ward, S. Lamboley, Tetrahedron 1995, 51, 9393-9412;
72. d) I. Paterson, J. D. Smith, R. A. Ward, Tetrahedron 1995, 51, 9413-9436;
73. e) I. Paterson, R. A. Ward, J. D. Smith, J. G. Gumming, K.-S. Yeung, Tetrahedron 1995, 51, 9437-9466;
74. f) I. Paterson, K.-S. Yeung, R. A. Ward, J. D. Smith, J. G. Cumming, S. Lamboley, Tetrahedron 1995, 51, 9467-9486;
75. for a later total synthesis of swinholide A, see: g) K. C. Nicolaou, K. Ajito, A. P. Patron, H. Khatuya, P. K. Richter, P. Bertinato, J. Am. Chem. Soc. 1996, 118, 3059-3060;
76. h) K. C. Nicolaou, A. P. Patron, K. Ajito, P. K. Richter, H. Khatuya, P. Bertinato, R. A. Miller, M. J. Tomaszewski, Chem. Eur. J. 1996, 2, 847-868; for a review of these two syntheses, see: K. C. Nicolaou, S. A. Snyder, Classics in Total Synthesis II: More Targets, Strategies, Methods, Wiley-VCH, Weinheim, 2003, chap. 3, p. 639.
77. h) K. C. Nicolaou, A. P. Patron, K. Ajito, P. K. Richter, H. Khatuya, P. Bertinato, R. A. Miller, M. J. Tomaszewski, Chem. Eur. J. 1996, 2, 847-868; for a review of these two syntheses, see: K. C. Nicolaou, S. A. Snyder, Classics in Total Synthesis II: More Targets, Strategies, Methods, Wiley-VCH, Weinheim, 2003, chap. 3, p. 639.
78. L. Ramachandra Row, K. S. Reddy, N. S. Sarma, T. Matsuura, R. Nakashima, Phytochemistry 1980, 19, 1175-1181.
79. a) B. Makino, M. Kawai, Y. Iwata, H. Yamamura, Y. Butsugan, K. Ogawa, M. Hayashi, Bull. Chem. Soc. Jpn. 1995, 68, 219-226;
80. for the structural revision of another member of this family, see: b) B. Makino, M. Kawai, T. Ogura, M. Nakanishi, H. Yamamura, Y. Butsugan, J. Nat. Prod. 1995, 55, 1668-1674;
81. for the structural revision of another physalin, whose proposed structure was based on a misassigned degradation product, see: c) M. Kawai, T. Ogura, Y. Butsugan, T. Taga, M. Hayashi, Tetrahedron 1991, 47, 2103-2110.
82. T. H. Al-Tel, M. H. A. Zarga, S. S. Sabri, M. Feroz, N. Fatima, Z. Shah, Atta-Ur-Rahman, Phytochemistry 1991, 30, 3081-3085.
83. A. V. Kalinin, V. Snieckus, Tetrahedron Lett. 1998, 39, 4999-5002. This revised structure is that of isoeugenetin methyl ether, a derivative of the natural product isoeugenetin that had been prepared nearly fifty years earlier: a) H. Schmid, A. Bolleter, Helv. Chim. Acta 1949, 32, 1358-1360;
84. A. V. Kalinin, V. Snieckus, Tetrahedron Lett. 1998, 39, 4999-5002. This revised structure is that of isoeugenetin methyl ether, a derivative of the natural product isoeugenetin that had been prepared nearly fifty years earlier: a) H. Schmid, A. Bolleter, Helv. Chim. Acta 1949, 32, 1358-1360;
85. b) H. Schmid, A. Bolleter, Helv. Chim. Acta 1950, 33, 917-922.
86. H. Greger, O. Hofer, H. Kählig, G. Wurz, Tetrahedron 1992, 48, 1209-1218.
87. W. M. Johnson, S. W. Littler, C. R. Strauss, Aust. J. Chem. 1994, 47, 751-756; for a later total synthesis of sinharine and a discussion of the original misassignment, see: S. Hinterberger, O. Hofer, H. Greger, Tetrahedron 1994, 50, 6279-6286.
88. W. M. Johnson, S. W. Littler, C. R. Strauss, Aust. J. Chem. 1994, 47, 751-756; for a later total synthesis of sinharine and a discussion of the original misassignment, see: S. Hinterberger, O. Hofer, H. Greger, Tetrahedron 1994, 50, 6279-6286.
89. O. M. Cóbar, A. D. Rodriguez, O. L. Padilla, J. A. Sánchez, J. Org. Chem. 1997, 62, 7183-7188.
90. Y.-P. Shi, A. D. Rodríguez, O. L. Padilla, J. Nat. Prod. 2001, 64, 1439-1443.
91. I. Kubo, S. P. Tanis, Y.-W. Lee, I. Miura, K. Nakanishi, A. Chapya, Heterocycles 1976, 5, 485-498.
92. M. S. Rajab, J. K. Rugutt, F. R. Fronczek, N. H. Fischer, J. Nat. Prod. 1997, 60, 822-825.
93. J. Rodríguez, B. M. Peters, L. Kurz, R. C. Schatzman, D. McCarley, L. Lou, P. Crews, J. Am. Chem. Soc. 1993, 115, 10436-10437.
94. J. Rodríguez, P. Crews, Tetrahedron Lett. 1994, 35, 4719-4722.
95. F. Balza, S. Tachibana, H. Barrios, G. H. N. Towers, Phytochemistry 1991, 30, 1613-1614.
96. a) G. I. Georg, S. R. Gollapudi, G. L. Grunewald, C. W. Gunn, R. H. Himes, B. K. Rao, X.-Z. Liang, Y. W. Mirhom, L. A. Mitscher, D. G. Vander Velde, Q.-M. Ye, Bioorg. Med. Chem. Lett. 1993, 3, 1345-1348;
97. b) G. I. Georg, Z. S. Cheruvallath, D. Vander Velde, Q.-M. Ye, L. A. Mitscher, Bioorg. Med. Chem. Lett. 1993, 3, 1349-1350;
98. for a slightly later publication leading to the same structural revision based on X-ray crystallographic analysis of a related compound, see: c) G. Appendino, L. Barboni, P. Gariboldi, E. Bombardelli, B. Gabetta, D. Viterbo, J. Chem. Soc. Chem. Commun. 1993, 1587-1589;
99. in concurrent work, a group (which included some of the initial isolation chemists) identified the transpositon of the acetate and benzoate units originally at C7 and C10, respectively, but not the constitutional change: d) A. Chu, J. Zajicek, G. H. N. Towers, C. M. Soucy-Breau, N. G. Lewis, R. Croteau, Phytochemistry 1993, 34, 269-271.
100. a) U. Renner, H. Fritz, Helv. Chim. Acta 1965, 48, 308-317;
101. for the earlier report of the isolation of isoschizogamine, see: b) U. Renner, P. Kernweisz, Experientia 1963, 19, 244-246.
102. J. Hájícek, J. Taimr, M. Budesínsky, Tetrahedron Lett. 1998, 39, 505-508.
103. J. L. Hubbs, C. H. Heathcock, Org. Lett. 1999, 1, 1315-1317.
104. a) Y. Kuroda, M. Okuhara, T. Goto, M. Yamashita, E. Iguchi, M. Kohsaka, H. Aoki, H. Imanaka, J. Antibiot. 1980, 33, 259-266;
105. b) Y. Kuroda, M. Okuhara, T. Goto, M. Okamoto, M. Yamashita, M. Kohsaka, H. Aoki, H. Imanaka, J. Antibiot. 1980, 33, 267-271.
106. a) N. Yasuda, K. Sakane, J. Antibiot. 1991, 44, 801-802.
107. Interestingly, the structure of FR900148 was questioned earlier based on the isolation of a potential biosynthetic precursor, but was not revised: b) L. Chaiet, B. H. Arison, R. L. Monaghan, J. P. Springer, J. L. Smith, S. B. Zimmerman, J. Antibiot. 1984, 37, 207-210.
108. J. Cáceres, M. E. Rivera, A. D. Rodriguez, Tetrahedron 1990, 40, 341-348.
109. a) J. Shin, W. Fenical, J. Org. Chem. 1991, 56, 3392-3398;
110. for a follow-up article by the original isolation chemists on the structural assignment, see: b) A. D. Rodriguez, A. L. Acosta, H. Dhasmana, J. Nat. Prod. 1993, 56, 1843-1849.
111. a) E. J. Corey, R. S. Kania, Tetrahedron Lett. 1998, 39, 741-744;
112. for a later total synthesis of palominol, see: b) H. Miyaoka, Y. Isaji, H. Mitome, Y. Yamada, Tetrahedron 2003, 59, 61-75.
113. a) J. Kobayashi, M. Ishibashi, H. Hirota, J. Nat. Prod. 1991, 54, 1435-1439;
114. for the original publication on the isolation, see: b) J. Kobayashi, M. Ishibashi, H. Nakamura, Y. Ohizumi, T. Yamasu, T. Sasaki, Y. Hirata, Tetrahedron Lett. 1986, 27, 5755-5758;
115. for a review on this family of natural products, see: c) M. Ishibashi, J. Kobayashi, Heterocycles 1997, 44, 543-572.
116. a) B. M. Trost, P. E. Harrington, J. Am. Chem. Soc. 2004, 126, 5028-5029;
117. for earlier syntheses of the originally proposed structure, see: b) H. W. Lam, G. Pattenden, Angew. Chem. 2002, 114, 526-529; Angew. Chem. Int. Ed. 2002, 41, 508-511;
118. for earlier syntheses of the originally proposed structure, see: b) H. W. Lam, G. Pattenden, Angew. Chem. 2002, 114, 526-529; Angew. Chem. Int. Ed. 2002, 41, 508-511;
119. c) R. E. Maleczka, L. R. Terrell, F. Geng, J. S. Ward, Org. Lett. 2002, 4, 2841-2844;
120. d) B. M. Trost, J. D. Chisholm, S. T. Wrobleski, M. Jung, J. Am. Chem. Soc. 2002, 124, 12420-12421.
121. M. A. M. Maciel, A. C. Pinto, S. N. Brabo, M. N. Da Silva, Phytochemistry 1998, 49, 823-828.
122. R. B. Grossman, R. M. Rasne, Org. Lett. 2001, 3, 4027-4030.
123. a) E. Selva, G. Beretta, N. Montanini, G. S. Saddler, L. Gastaldo, P. Ferrari, R. Lorenzetti, P. Landini, F. Ripamonti, B. P. Goldstein, M. Berti, L. Montanaro, M. Denaro, J. Antibiot. 1991, 44, 693-701;
124. b) J. Kettenring, L. Colombo, P. Ferrari, P. Tavecchia, M. Nebuloni, K. Vékey, G. G. Gallo, E. Selva, J. Antibiot. 1991, 44, 702-715.
125. a) P. Tavecchia, P. Gentili, M. Kurz, C. Sottani, R. Bonfichi, S. Lociuro, E. Selva, J. Antibiot. 1994, 47, 1564-1567;
126. for the full account of this structural revision, see: b) P. Tavecchia, P. Gentili, M. Kurz, C. Sottani, R. Bonfichi, E. Selva, S. Lociuro, E. Restelli, R. Ciabatti, Tetrahedron 1995, 51, 4867-4890.
127. For synthetic work which nearly reached this target molecule, see: T. Suzuki, K. Nagasaki, K. Okumura, C. Shin, Heterocycles 2001, 55, 835-840.
128. Y. Asakawa, A. Yamamura, T. Waki, T. Takemoto, Phytochemistry 1980, 19, 603-607.
129. M. Tori, K. Nakashima, M. Toyota, Y. Asakawa, Tetrahedron Lett. 1993, 34, 3751-3752.
130. A. Buske, S. Busemann, J. Mühlbacher, J. Schmidt, A. Porzel, G. Bringmann, G. Adam, Tetrahedron 1999, 55, 1079-1086.
131. G. Bringmann, J. Schlauer, H. Rischer, M. Wohlfarth, J. Mühlbacher, A. Buske, A. Porzel, J. Schmidt, G. Adam, Tetrahedron 2000, 56, 3691-3695.
132. S. Ômura, A. Nakagawa, H. Yamada, T. Hata, A. Furusaki, T. Watanabe, Chem. Pharm. Bull. 1973, 21, 931-940.
133. S. J. Gould, N. Tamayo, C. R. Melville, M. C. Cone, J. Am. Chem. Soc. 1994, 116, 2207-2208.
134. S. Mithani, G. Weeratunga, N. J. Taylor, G. I. Dmitrienko, J. Am. Chem. Soc. 1994, 116, 2209-2210.
135. a) J. E. Leet, D. R. Schroeder, S. J. Hofstead, J. Golik, K. L. Colson, S. Huang, S. E. Klohr, T. W. Doyle, J. A. Matson, J. Am. Chem. Soc. 1992, 114, 7946-7948;
136. b) J. E. Leet, D. R. Schroeder, D. R. Langley, K. L. Colson, S. Huang, S. E. Klohr, M. S. Lee, J. Golik, S. J. Hofstead, T. W. Doyle, J. A. Matson, J. Am. Chem. Soc. 1993, 115, 8432-8443.
137. S. Kawata, S. Ashizawa, M. Hirama, J. Am. Chem. Soc. 1997, 119, 12012-12013.
138. The Myers group has synthesized the complete kedarcidin chromophore aglycon enantioselectively in protected form, thus verifying its revised connectivities and stereostructure: A. G. Myers, P. C. Hogan, A. R. Hurd, S. D. Goldberg, Angew. Chem. 2002, 114, 1104-1109; Angew. Chem. Int. Ed. 2002, 41, 1062-1067.
139. The Myers group has synthesized the complete kedarcidin chromophore aglycon enantioselectively in protected form, thus verifying its revised connectivities and stereostructure: A. G. Myers, P. C. Hogan, A. R. Hurd, S. D. Goldberg, Angew. Chem. 2002, 114, 1104-1109; Angew. Chem. Int. Ed. 2002, 41, 1062-1067.
140. D. G. Corley, G. E. Rottinghaus, M. S. Tempesta, Tetrahedron Lett. 1986, 27, 427-430.
141. F. E. Ziegler, A. Nangia, M. S. Tempesta, Tetrahedron Lett. 1988, 29, 1665-1668.
142. a) F. E. Ziegler, C. A. Metcalf, G. Schulte, Tetrahedron Lett. 1992, 33, 3117-3120;
143. for the full account of this total synthesis, see: b) F. E. Ziegler, C. A. Metcalf, A. Nangia, G. Schulte, J. Am. Chem. Soc. 1993, 115, 2581-2589.
144. T. Komoda, Y. Sugiyama, N. Abe, M. Imachi, H. Hirota, A. Hirota, Tetrahedron Lett. 2003, 44, 1659-1661.
145. T. Komoda, Y. Sugiyama, N. Abe, M. Imachi, H. Hirota, H. Koshino, A. Hirota, Tetrahedron Lett. 2003, 44, 7417-7419.
146. N. González, J. Rodríguez, C. Jiménez, J. Org. Chem. 1999, 64, 5705-5707.
147. H. Kiyota, D. J. Dixon, C. K. Luscombe, S. Hettstedt, S. V. Ley, Org. Lett. 2002, 4, 3223-3226.
148. C. Kan-Fan, J.-C. Quirion, I. R. C. Bick, H.-P. Husson, Tetrahedron 1988, 44, 1651-1660.
149. a) R. Güller, M. Dobler, H.-J. Borschberg, Helv. Chim. Acta 1991, 74, 1636-1642;
150. for the full account of this total synthesis, see: b) J.-C. Quirion, H.-P. Husson, C. Kan, O. Laprévote, A. Chiaroni, C. Riche, S. Burkard, H.-J. Borschberg, I. R. C. Bick, J. Org. Chem. 1992, 57, 5848-5851;
151. for total syntheses of related alkaloids whose structures were also revised, see: c) S. Burkard, H.-J. Borschberg, Helv. Chim. Acta 1991, 74, 275-289;
152. d) R. Güller, H.-J. Borschberg, Helv. Chim. Acta 1991, 74, 1643-1653.
153. F. A. Macías, R. M. Varela, A. Torres, R. M. Oliva, J. M. G. Molinillo, Phytochemistry 1998, 48, 631-636.
154. H. Takikawa, K. Isono, M. Sasaki, F. A. Macías, Tetrahedron Lett. 2003, 44, 7023-7025.
155. W. C. Taylor, S. Toth, Aust. J. Chem. 1997, 50, 895-902.
156. M. Arno, M. A. González, R. J. Zaragozá, J. Org. Chem. 2003, 68, 1242-1251.
157. E. Sakuno, K. Yabe, T. Hamasaki, H. Nakajima, J. Nat. Prod. 2000, 63, 1677-1678.
158. P. Wipf, A.D. Kerekes, J. Nat. Prod. 2003, 66, 716-718. TAEMC161 is actually the phytotoxin natural product viridiol, which had been isolated and characterized more than 30 years earlier: J. S. Moffatt, J. D. Bu'Lock, T. H. Yuen, Chem. Commun. 1969, 839.
159. P. Wipf, A.D. Kerekes, J. Nat. Prod. 2003, 66, 716-718. TAEMC161 is actually the phytotoxin natural product viridiol, which had been isolated and characterized more than 30 years earlier: J. S. Moffatt, J. D. Bu'Lock, T. H. Yuen, Chem. Commun. 1969, 839.
160. W. R. Kem, K. N. Scott, J. H. Duncan, Experientia 1976, 32, 684-686.
161. J. A. Zoltewicz, M. P. Cruskie, Tetrahedron 1995, 51, 11401-11410.
162. a) M. P. Cruskie, J. A. Zoltewicz, K. A. Abboud, J. Org. Chem. 1995, 60, 7491-7495;
163. for a later total synthesis of nemertelline, see: b) A. Bouillon, A. S. Voisin, A. Robic, J.-C. Lancelot, V. Collot, S. Rault, J. Org. Chem. 2003, 68, 10178-10180.
164. N. Lindquist, W. Fenical, Tetrahedron Lett. 1989, 30, 2735-2738.
165. a) M. S. Congreve, A. B. Holmes, A. B. Hughes, M. G. Looney, J. Am. Chem. Soc. 1993, 115, 5815-5816;
166. for a later total synthesis of ascidiatrienolide A, see: b) A. Fürstner, M. Schiede, Adv. Synth. Catal. 2002, 344, 657-665.
167. P. S. Parameswaran, C. G. Naik, S. Y. Kamat, B. N. Pramanik, Indian J. Chem. Sect. B 1998, 37, 1258-1263.
168. N. Saito, H. Sakai, K. Suwanborirux, S. Pummangura, A. Kubo, Heterocycles 2001, 55, 21-28. These researchers were the first to note that renieramycin H is identical to cribrostatin 4, a compound isolated independently by Pettit et al. and characterized by using X-ray crystallographic analysis: G. R. Pettit, J. C. Knight, J. C. Collins, D. L. Herald, R. K. Pettit, M. R. Boyd, V. G. Young, J. Nat. Prod. 2000, 63, 793-798.
169. N. Saito, H. Sakai, K. Suwanborirux, S. Pummangura, A. Kubo, Heterocycles 2001, 55, 21-28. These researchers were the first to note that renieramycin H is identical to cribrostatin 4, a compound isolated independently by Pettit et al. and characterized by using X-ray crystallographic analysis: G. R. Pettit, J. C. Knight, J. C. Collins, D. L. Herald, R. K. Pettit, M. R. Boyd, V. G. Young, J. Nat. Prod. 2000, 63, 793-798.
170. a) B. M. Degnan, C. J. Hawkins, M. F. Lavin, E. J. McCaffrey, D. L. Parry, D. J. Watters, J. Med. Chem. 1989, 32, 1354-1359;
171. for the original isolation, see: b) D. Gouiffès, S. Moreau, N. Helbecque, J. L. Bernier, J. P. Hénichart, Y. Barbin, D. Laurent, J. F. Verbist, Tetrahedron 1988, 44, 451-459.
172. Bistramide A has also been named bistratene A; for a later isolation of other family members, see: c) J.-F. Biard, C. Roussakis, J.-M. Kornprobst, D. Gouiffes-Barbin, J.-F. Verbist, P. Cotelle, M. P. Foster, C. M. Ireland, C. Debitus, J. Nat. Prod. 1994, 57, 1336-1345.
173. M. P. Foster, C. L. Mayne, R. Dunkel, R. J. Pugmire, D. M. Grant, J.-M. Kornprobst, J.-F. Verbist, J.-F. Biard, C. M. Ireland, J. Am. Chem. Soc. 1992, 114, 1110-1111.
174. a) P. Welzel, F.-J. Witteler, D. Müller, W. Riemer, Angew. Chem. 1981, 93, 130-132; Angew. Chem. Int. Ed. Engl. 1981, 20, 121-123;
175. a) P. Welzel, F.-J. Witteler, D. Müller, W. Riemer, Angew. Chem. 1981, 93, 130-132; Angew. Chem. Int. Ed. Engl. 1981, 20, 121-123;
176. b) P. Welzel, B. Wietfeld, F. Kunisch, T. Schubert, K. Robert, H. Duddeck, D. Müller, G. Huber, J. E. Maggio, D. H. Williams, Tetrahedron 1983, 39, 1583-1591.
177. H.-W. Fehlhaber, M. Girg, G. Seibert, K. Robert, P. Welzel, Y. Van Heijenoort, J. Van Heijenoort, Tetrahedron 1990, 46, 1557-1568.
178. G. R. Pettit, C. L. Herald, Y. Kamano, J. Org. Chem. 1983, 48, 5354-5356.
179. a) D. E. Schaufelberger, G. N. Chmurny, J. A. Beutler, M. P. Koleck, A. B. Alvarado, B. W. Schaufelberger, G. M. Muschik, J. Org. Chem. 1991, 56, 2895-2900;
180. b) G. N. Chmurny, M. P. Koleck, B. D. Hilton, J. Org. Chem. 1992, 57, 5260-5264.
181. K. Ohmori, Y. Ogawa, T. Obitsu, Y. Ishikawa, S. Nishiyama, S. Yamamura, Angew. Chem. 2000, 112, 2376-2379; Angew. Chem. Int. Ed. 2000, 39, 290-2294.
182. K. Ohmori, Y. Ogawa, T. Obitsu, Y. Ishikawa, S. Nishiyama, S. Yamamura, Angew. Chem. 2000, 112, 2376-2379; Angew. Chem. Int. Ed. 2000, 39, 290-2294.
183. a) J.-J. Chen, S.-X. Qiu, Z.-X. Zhang, J. Zhou, Acta Bot. Yunnanica 1989, 11, 203-208;
184. b) S.-X. Qiu, Z.-X. Zhang, J. Zhou, Acta Bot. Sin. 1990, 32, 936-942.
185. S.-X. Qiu, L.-Z. Lin, Y. Nan, P. Lin, J.-J. Chen, Z.-X. Zhang, J. Zhou, G. A. Cordell, Phytochemistry 1995, 40, 917-921.
186. W. W. Harding, RA. Lewis, H. Jacobs, S. McLean, W. F. Reynolds, L.-L. Tay, J.-P Yang, Tetrahedron Lett. 1995, 36, 9137-9140.
187. Three groups synthesized the proposed structure of glabrescol independently at roughly the same time: a) H. Hioki, C. Kanehara, Y. Ohnishi, Y. Umemori, H. Sakai, S. Yoshio, M. Matsushita, M. Kodama, Angew. Chem. 2000, 112, 2652-2654; Angew. Chem. Int. Ed. 2000, 39, 2552-2554;
188. Three groups synthesized the proposed structure of glabrescol independently at roughly the same time: a) H. Hioki, C. Kanehara, Y. Ohnishi, Y. Umemori, H. Sakai, S. Yoshio, M. Matsushita, M. Kodama, Angew. Chem. 2000, 112, 2652-2654; Angew. Chem. Int. Ed. 2000, 39, 2552-2554;
189. b) Y. Morimoto, T. Iwai, T. Kinoshita, J. Am. Chem. Soc. 2000, 122, 7124-7125;
190. c) Z. Xiong, E. J. Corey, J. Am. Chem. Soc. 2000, 122, 4831-4832.
191. Reference [108b] included a revision of the structure and the first reported total synthesis of the true glabrescol. A few months later, a second and more efficient total synthesis of the revised structure was reported: d) Z. Zhong, E. J. Corey, J. Am. Chem. Soc. 2000, 122, 9328-9329;
192. for an attempt to use molecular modeling to predict the correct structure of glabrescol, see: e) B. R. Bellenie, J. M. Goodman, Tetrahedron Lett. 2001, 42, 7477-7479.
193. For the original isolation and elucidation of parts of the structure, see: a) M. Seki-Asano, T. Okazaki, M. Yamagishi, N. Sakai, K. Kanada, K. Mizoue, J. Antibiot. 1994, 47, 1226-1233;
194. b) M. Seki-Asano, Y. Tsuchida, K. Hanada, K. Mizoue, J. Antibiot. 1994, 47, 1234-1241;
195. for the assignment of the stereostructure FD-891, see: c) T. Eguchi, K. Kobayashi, H. Uekusa, Y. Ohashi, K. Mizoue, Y. Matsushima, K. Kakinuma, Org. Lett. 2002, 4, 3383-3386.
196. T. Eguchi, K. Yamamoto, K. Mizoue, K. Kakinuma, J. Antibiot. 2004, 57, 156-157.
197. The revised structure is exactly the same as that of the natural product BE-45653: H. Ogawa, S. Nakajima, H. Suzuki, K. Ojiri, H. Suda, Jpn. Kokai Tokkyo Koho, 1997, 0987285.
198. a) M. R. Prinsep, F. R. Caplan, R. E. Moore, G. M. L. Patterson, C. D. Smith, J. Am. Chem. Soc. 1992, 114, 385-387;
199. b) M. R. Prinsep, G. M. L. Patterson, L. K. Larsen, C. D. Smith, Tetrahedron 1995, 51, 10523-10530.
200. a) T. G. Minehan, Y. Kishi, Angew. Chem. 1999, 111, 972-975; Angew. Chem. Int. Ed. 1999, 38, 923-925;
201. a) T. G. Minehan, Y. Kishi, Angew. Chem. 1999, 111, 972-975; Angew. Chem. Int. Ed. 1999, 38, 923-925;
202. b) T. G. Minehan, L. Cook-Blumberg, Y. Kishi, M. R. Prinsep, R. E. Moore, Angew. Chem. 1999, 111, 975-977; Angew. Chem. Int. Ed. 1999, 38, 926-928.
203. b) T. G. Minehan, L. Cook-Blumberg, Y. Kishi, M. R. Prinsep, R. E. Moore, Angew. Chem. 1999, 111, 975-977; Angew. Chem. Int. Ed. 1999, 38, 926-928.
204. W. Wang, Y. Kishi, Org. Lett. 1999, 1, 1129-1132.
205. For the original isolation and elucidation of parts of the structure, see: a) K. S. Lam, G. A. Hesler, J. M. Mattei, S. W. Mamber, S. Forenza, K. Tomita, J. Antibiot. 1990, 43, 956-960;
206. b) J. E. Leet, D. R. Schroeder, B. S. Krishnan, J. A. Matson, J. Antibiot. 1990, 43, 961-966;
207. for the assignment of the stereostructure of himastatin, see: c) J. E. Leet, D. R. Schroeder, J. Golik, J. A. Matson, T. W. Doyle, K. S. Lam, S. E. Hill, M. S. Lee, J. L. Whitney, B. S. Krishnan, J. Antibiot. 1996, 49, 299-311.
208. a) T. M. Kamenecka, S. J. Danishefsky, Angew. Chem. 1998, 110, 3164-3166; Angew. Chem. Int. Ed. 1998, 37, 2993-2995;
209. a) T. M. Kamenecka, S. J. Danishefsky, Angew. Chem. 1998, 110, 3164-3166; Angew. Chem. Int. Ed. 1998, 37, 2993-2995;
210. b) T. M. Kamenecka, S. J. Danishefsky, Angew. Chem. 1998, 110, 3166-3168; Angew. Chem. Int. Ed. 1998, 37, 2995-2998;
211. b) T. M. Kamenecka, S. J. Danishefsky, Angew. Chem. 1998, 110, 3166-3168; Angew. Chem. Int. Ed. 1998, 37, 2995-2998;
212. for the full account of this work, see: c) T. M. Kamenecka, S. J. Danishefsky, Chem. Eur. J. 2001, 7, 41-63.
213. R.-s. Xu, J. K. Snyder, K. Nakanishi, J. Am. Chem. Soc. 1984, 106, 734-736.
214. Q. Cheng, J. K. Snyder, J. Org. Chem. 1988, 53, 4562-4567; for an earlier total synthesis of the originally proposed structure of robustadial A, see: K. Lal, E. A. Zarate, W. J. Youngs, R. G. Salomon, J. Am. Chem. Soc. 1986, 108, 1311-1312.
215. Q. Cheng, J. K. Snyder, J. Org. Chem. 1988, 53, 4562-4567; for an earlier total synthesis of the originally proposed structure of robustadial A, see: K. Lal, E. A. Zarate, W. J. Youngs, R. G. Salomon, J. Am. Chem. Soc. 1986, 108, 1311-1312.
216. a) R. G. Salomon, K. Lal, S. M. Mazza, E. A. Zarate, W. J. Youngs, J. Am. Chem. Soc. 1988, 110, 5213-5214;
217. for a full account of this synthesis, see: b) R. G. Salomon, S. M. Mazza, K. Lal, J. Org. Chem. 1989, 54, 1562-1570;
218. for more recent total syntheses of the robustadials, see: c) S. Koser, H. M. R. Hoffmann, D. J. Williams, J. Org. Chem. 1993, 58, 6163-6165;
219. d) S. Bissada, C. K. Lau, M. A. Bernstein, C. Dufresne, Can. J. Chem. 1994, 72, 1866-1869;
220. e) I. R. Aukrust, L. Skatteboel, Acta Chem. Scand. 1996, 50, 132-140;
221. for a synthesis of robustadial A dimethyl ether, see: f) M. Majewski, G. Bantle, Tetrahedron Lett. 1989, 30, 6653-6656;
222. g) M. Majewski, N. M. Irvine, G. W. Bantle, J. Org. Chem. 1994, 59, 6697-6702.
223. For the original isolation and elucidation of parts of the structure, see: a) G. R. Pettit, Z. A. Cichacz, F. Gao, M. R. Boyd, J. M. Schmidt J. Chem. Soc. Chem. Commun. 1994, 1111-1112;
224. for the determination of parts of the stereostructure of dictyostatin 1, see: b) G. R. Pettit, Z. A. Cichacz, US Patent 5430053,1995 [Chem. Abst. 1995, 123, 139562];
225. for some information on its biological activity, see: c) R. A. Isbrucker, J. Cummins, S. A. Pomponi, R. E. Longley, A. E. Wright, Biochem. Pharmacol. 2003, 66, 75-82.
226. I. Paterson, R. Britton, O. Delgado, A. E. Wright, Chem. Commun. 2004, 632-633.
227. J. F. Biard, S. Guyot, C. Roussakis, J. F. Verbist, J. Vercauteren, J. F. Weber, K. Boukef, Tetrahedron Lett. 1994, 35, 2691-2694.
228. a) H. Abe, S. Aoyagi, C. Kibayashi, J. Am. Chem. Soc. 2000, 122, 4583-4592;
229. b) H. Abe, S. Aoyagi, C. Kibayashi, Angew. Chem. 2002, 114, 3143-3146; Angew. Chem. Int. Ed. 2002, 41, 3017-3020;
230. b) H. Abe, S. Aoyagi, C. Kibayashi, Angew. Chem. 2002, 114, 3143-3146; Angew. Chem. Int. Ed. 2002, 41, 3017-3020;
231. for the full account of this total synthesis, see: c) C. Kibayashi, S. Aoyagi, H. Abe, Bull. Chem. Soc. Jpn. 2003, 76, 2059-2074;
232. for earlier total syntheses of the proposed structure of lepadiformine that did not point to a definitive structural alternative, see: d) W. H. Pearson, Y. Ren, J. Org. Chem. 1999, 64, 688-689;
233. e) K. M. Werner, J. M. de los Santos, S. M. Weinreb, M. Shang, J. Org. Chem. 1999, 64, 686-687;
234. f) K. M. Werner, J. M. de los Santos, S. M. Weinreb, M. Shang, J. Org. Chem. 1999, 64, 4865-4873;
235. g) H. Abe, S. Aoyagi, C. Kibayashi, Tetrahedron Lett. 2000, 41, 1205-1208;
236. for later total syntheses of the revised structure of lepadiformine, see: h) P. Sun, C. Sun, S. M. Weinreb, Org. Lett. 2001, 3, 3507-3510;
237. T. J. Greshock, R. L. Funk, Org. Lett. 2001, 3, 3511-3514;
238. j) P. Sun, C. Sun, S. M. Weinreb, J. Org. Chem. 2002, 67, 4337-4345;
239. for a review of one of these research programs, see: k) S. M. Weinreb, Ace. Chem. Res. 2003, 36, 59-65.
240. A. R. Carroll, J. C. Coll, D. J. Bourne, J. K. MacLeod, T. M. Zabriskie, C. M. Ireland, B. F. Bowden, Aust. J. Chem. 1996, 49, 659-667.
241. a) P. Wipf, Y. Uto, J. Org. Chem. 2000, 65, 1037-1049;
242. for their synthesis of the originally proposed structure, see: b) P. Wipf, Y. Uto, Tetrahedron Lett. 1999, 40, 5165-5169;
243. for later total syntheses of the revised structure of trunkamide A, see: c) B. McKeever, G. Pattenden, Tetrahedron Lett. 2001, 42, 2573-2577;
244. d) B. McKeever, G. Pattenden, Tetrahedron 2003, 59, 2713-2727;
245. e) J. M. Caba, I. M. Rodriguez, I. Manzanares, E. Giralt, F. Albericio, J. Org. Chem. 2001, 66, 7568-7574.
246. J. Orjala, D. G. Nagle, V. L. Hsu, W. H. Gerwick, J. Am. Chem. Soc. 1995, 117, 8281-8282.
247. a) F. Yokokawa, H. Fujiwara, T. Shioiri, Tetrahedron Lett. 1999, 40, 1915-1916;
248. for the full account of this work, see: b) F. Yokokawa, H. Fujiwara, T. Shioiri, Tetrahedron 2000, 56, 1759-1775;
249. for earlier syntheses of the proposed structure of antillatoxin that did not lead to the proposal of a definitive structural alternative, see: c) F. Yokokawa; T. Shioiri, J. Org. Chem. 1998, 63, 8638-8639;
250. J. D. White, R. Hanselmann, D. J. Wardrop, J. Am. Chem. Soc. 1999, 121, 1106-1107.
251. S. Konetschny-Rapp, H.-W. Krell, U. Martin, World patent 96/ 11941, 1996 [Chem. Abst. 1996, 124, 315175].
252. S. Hanessian, M. Tremblay, J. F. W. Petersen, J. Am. Chem. Soc. 2004, 126, 6064-6071.
253. Y. Igarashi, K. Futamata, T. Fujita, A. Sekine, H. Senda, H. Naoki, T. Furumai, J. Antibiot. 2003, 56, 107-113.
254. M. E. Tichenor, D. B. Kastrinsky, D. L. Boger, J. Am. Chem. Soc. 2004, 126, 8396-8398; for earlier studies relating to the chemical biology of this interesting natural product, see: J. P. Parrish, D. B. Kastrinsky, S. E. Wolkenberg, Y. Igarashi, D. L. Boger, J. Am. Chem. Soc. 2003, 125, 10971-10976.
255. M. E. Tichenor, D. B. Kastrinsky, D. L. Boger, J. Am. Chem. Soc. 2004, 126, 8396-8398; for earlier studies relating to the chemical biology of this interesting natural product, see: J. P. Parrish, D. B. Kastrinsky, S. E. Wolkenberg, Y. Igarashi, D. L. Boger, J. Am. Chem. Soc. 2003, 125, 10971-10976.
256. For the correction of the two incorrect structures, see: a) L. Witte, L. Ernst, V. Wray, T. Hartmann, Phytochemistry 1992, 31, 1027-1028;
257. for the earlier misassignments, see: b) J. G. Urones, P. B. Barcala, I. S. Marcos, R. F. Moro, M. L. Esteban, A. F. Rodriguez, Phytochemistry 1988, 27, 1507;
258. F. Bohlmann, C. Zdero, J. Jakupovic, M. Grenz, V. Castro, R. M. King, H. Robinson, L. P. D. Vincent, Phytochemistry 1986, 25, 1151-1159;
259. see also: d) E. Roeder, Phytochemistry 1990, 29, 11-29.
260. For the correction of the two incorrect structures, see: a) H. Okamura, T. Iwagawa, M. Nakatani, Bull. Chem. Soc. Jpn. 1995, 65, 3465-3467;
261. for the earlier misassignments, see: b) Y. Takeda, H. Yamashita, T. Matsumoto, H. Terao, Phytochemistry 1993, 33, 713-715;
262. M. Uchida, Y. Koike, G. Kusano, Y. Kondo, S. Nozoe, C. Kabuto, T. Takemoto, Chem. Pharm. Bull. 1990, 28, 92-102;
263. M. Uchida, G. Kusano, Y. Kondo, S. Nozoe, T. Takemoto, Heterocycles 1978, 9, 139-144.
264. T. C. Fleischer, R. D. Waigh, P. G. Waterman, J. Nat. Prod. 1997, 60, 1054-1056.
265. K. I. Booker-Milburn, H. Jenkins, J. P. H. Charmant, P. Mohr, Org. Lett. 2003, 5, 3309-3312.
266. M. F. Rodríguez Brasco, A. M. Seldes, J. A. Palermo, Org. Lett. 2001, 3, 1415-1417.
267. K. Inanaga, K. Takasu, M. Ihara, J. Am. Chem. Soc. 2004, 126, 1352-1353.
268. T. Hashimoto, S. Kondo, H. Naganawa, T. Takita, K. Maeda, H. Umezawa, J. Antibiot. 1974, 27, 86-87.
269. M. E. Bunnage, T. Ganesh, I. B. Masesane, D. Orton, P. G. Steel, Org. Lett. 2003, 5, 239-242.
270. N. J. Sun, S. H. Woo, J. M. Cassady, R. M. Snapka, J. Nat. Prod. 1998, 67, 362-366.
271. J. B. Perales, N. F. Makino, D. L. Van Vranken, J. Org. Chem. 2002, 67, 6711-6717.
272. S. N. Kazmi, Z. Ahmed, W. Ahmed, A. Malik, Heterocycles 1989, 29, 1901-1906.
273. D. L. Comins, X. Zheng, R. R. Goehring, Org. Lett. 2002, 4, 1611-1613.
274. A. R. Carroll, W. C. Taylor, Aust. J. Chem. 1991, 44, 1615-1626.
275. M. K. Gurjar, J. Cherian, C. V. Ramana, Org. Lett. 2004, 6, 317-319.
276. N. Fukamiya, M. Okano, M. Miyamoto, K. Tagahara, K.-H. Lee, J. Nat. Prod. 1992, 55, 468-475.
277. J. M. VanderRoest, P. A. Grieco, J. Org. Chem. 1996, 61, 5316-5325.
278. R. Pummerer, H. Puttfarcken, P. Schopflocher, Ber. Dtsch. Chem. Ges. B 1925, 58, 1808-1820.
279. a) D. H. R. Barton, A. M. Deflorin, O. E. Edwards, Chem. Ind. 1955, 1039;
280. b) D. H. R. Barton, A. M. Deflorin, O. E. Edwards, J. Chem. Soc. 1956, 530-532; for an engaging overview of this work, see: D. H. R. Barton, Half a Century of Free Radical Chemistry, Cambridge University Press, Cambridge, 1993, p. 164.
281. b) D. H. R. Barton, A. M. Deflorin, O. E. Edwards, J. Chem. Soc. 1956, 530-532; for an engaging overview of this work, see: D. H. R. Barton, Half a Century of Free Radical Chemistry, Cambridge University Press, Cambridge, 1993, p. 164.
282. a) E. Brochmann-Hanssen, B. Nielsen, Tetrahedron Lett. 1965, 7, 1271-1274;
283. b) A. R. Battersby, G. W. Evans, Tetrahedron Lett. 1965, 7, 1275-1278.
284. D. H. R. Barton, B. D. Brown, D. D. Ridley, D. A. Widdowson, A. J. Keys, C. J. Leaver, J. Chem. Soc. Perkin Trans, 1 1975, 2069-2076;
285. see also: A. J. Keys, C. J. Leaver, D. H. R. Barton, B. D. Brown, D. A. Widdowson, Nature 1971, 232, 423-424.
286. a) F. W. Lichtenthaler, K. Nakamura, J. Klotz, Angew. Chem. 2003, 115, 6019-6023; Angew. Chem. Int. Ed. 2003, 42, 5838-5843;
287. a) F. W. Lichtenthaler, K. Nakamura, J. Klotz, Angew. Chem. 2003, 115, 6019-6023; Angew. Chem. Int. Ed. 2003, 42, 5838-5843;
288. b) F. W. Lichtenthaler, J. Klotz, K. Nakamura, Tetrahedron: Asymmetry 2003, 14, 3973-3986.
289. For the initial assignment based on X-ray crystallography and other methods, see: a) J. S. Webb, D. B. Cosulich, J. H. Mowat, J. B. Patrick, R. W. Broschard, W. E. Meyer, R. P. Williams, C. F. Wolf, W. Fulmor, C. Pidacks, J. E. Lancaster, J. Am. Chem. Soc. 1962, 84, 3185-3187;
290. b) J. S. Webb, D. B. Cosulich, J. H. Mowat, J. B. Patrick, R. W. Broschard, W. E. Meyer, R. P. Williams, C. F. Wolf, W. Fulmor, C. Pidacks, J. E. Lancaster, J. Am. Chem. Soc. 1962, 84, 3187-3188;
291. c) A. Tulinsky, J. Am. Chem. Soc. 1962, 84, 3188-3190;
292. A. Tulinsky, J. H. vanden Hende, J. Am. Chem. Soc. 1967, 89, 2905-2911.
293. a) U. Hornemann, M. J. Aikman, J. Chem. Soc. Chem. Commun. 1973, 88-89;
294. b) U. Hornemann, J. P. Kehrer, C. S. Nunez, R. L. Ranieri, J. Am. Chem. Soc. 1974, 96, 320-322.
295. N. Hirayama, K. Shirahata, Acta. Crystallogr. Sect. B 1987, 43, 555-559.
296. For a detailed account of the British-American penicillin project, see: The Chemistry of Penicillin (Eds.: H. T. Clarke, J. R. Johnson, R. Robinson), Princeton University Press, Princeton, 1949, p. 1094.
297. Interestingly, two attempts to synthesize penicillin from compounds of type 46 and 47 did lead to miniscule amounts of the natural product through an unanticipated rearrangement. However, the yield was too low for this method to replace fermentation as the primary source of the penicillin during the war.
298. J. W. Lown, C. C. Hanstock, J. Am. Chem. Soc. 1982, 104, 3213-3214.
299. a) M. Onda, Y. Konda, A. Hatano, T. Hata, S. Ômura, J. Am. Chem. Soc. 1983, 105, 6311-6312;
300. b) M. Onda, Y. Konda, A. Hatano, T. Hata, S. Ômura, Chem. Pharm. Bull. 1984, 32, 2995-3002.
301. M. E. Salvati, E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1992, 33, 3711-3714. These researchers were also the first to recognize problems with the molecular formula proposed earlier for carzinophilin (see: P. England, K. H. Chun, E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1990, 31, 2669-2672; E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1991, 32, 3807-3810)
302. M. E. Salvati, E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1992, 33, 3711-3714. These researchers were also the first to recognize problems with the molecular formula proposed earlier for carzinophilin (see: P. England, K. H. Chun, E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1990, 31, 2669-2672; E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1991, 32, 3807-3810)
303. M. E. Salvati, E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1992, 33, 3711-3714. These researchers were also the first to recognize problems with the molecular formula proposed earlier for carzinophilin (see: P. England, K. H. Chun, E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1990, 31, 2669-2672; E. J. Moran, R. W. Armstrong, Tetrahedron Lett. 1991, 32, 3807-3810)
304. and to recognize that carzinophilin is identical to azinomycin B, a compound isolated a few years earlier but thought, at the time, to have a different molecular formula: a) K. Nagaoka, M. Matsumoto, J. Oono, K. Yokoi, S. Ishizeki, T. Nakashima, J. Antibiot. 1986, 39, 1527-1532;
305. b) K. Yokoi, K. Nagaoka, T. Nakashima, Chem. Pharm. Bull. 1986, 34, 4554-4561.
306. For the total synthesis of azinomycin A, see: R. S. Coleman, J. Li, A. Navarro, Angew. Chem. 2001, 113, 1786-1789; Angew. Chem. Int. Ed. 2001, 40, 1736-1739; for the most advanced synthetic studies towards azinomycin B/carzinophilin, see: M. Hashimoto, M. Matsumoto, S. Terashima, Tetrahedron 2003, 59, 3019-3040 and ensuing publications in this series.
307. For the total synthesis of azinomycin A, see: R. S. Coleman, J. Li, A. Navarro, Angew. Chem. 2001, 113, 1786-1789; Angew. Chem. Int. Ed. 2001, 40, 1736-1739; for the most advanced synthetic studies towards azinomycin B/carzinophilin, see: M. Hashimoto, M. Matsumoto, S. Terashima, Tetrahedron 2003, 59, 3019-3040 and ensuing publications in this series.
308. For the total synthesis of azinomycin A, see: R. S. Coleman, J. Li, A. Navarro, Angew. Chem. 2001, 113, 1786-1789; Angew. Chem. Int. Ed. 2001, 40, 1736-1739; for the most advanced synthetic studies towards azinomycin B/carzinophilin, see: M. Hashimoto, M. Matsumoto, S. Terashima, Tetrahedron 2003, 59, 3019-3040 and ensuing publications in this series.
309. P. R. Zanno, I. Miura, K. Nakanishi, D. L. Elder, J. Am. Chem. Soc. 1975, 97, 1975-1977.
310. J. N. Hilton, H. B. Broughton, S. V. Ley, Z. Lidert, E. D. Morgan, H. S. Rzepa, R. N. Sheppard, J. Chem. Soc. Chem. Commun. 1985, 968-971.
311. a) H. B. Broughton, S. V. Ley, A. M. Z. Slawin, D. J. Williams, E. D. Morgan, J. Chem. Soc. Chem. Commun. 1986, 46-47;
312. b) W. Kraus, M. Bokel, A. Klenk, H. Pöhnl, Tetrahedron Lett. 1985, 26, 6435-6438;
313. for the full account of these final structural investigations, see: c) D. A. H. Taylor, Tetrahedron 1987, 43, 2779-2787;
314. C. J. Turner, M. S. Tempesta, R. B. Taylor, M. G. Zagorski, J. S. Termini, D. R. Schroeder, K. Nakanishi, Tetrahedron 1987, 43, 2789-2803;
315. e) J. N. Bilton, H. B. Broughton, P. S. Jones, S. V. Ley, Z. Lidert, E. D. Morgan, H. S. Rzepa, R. N. Sheppard, A. M. Z. Slawin, D. J. Williams, Tetrahedron 1987, 43, 2805-2815;
316. f) W. Kraus, M. Bokel, A. Bruhn, R. Cramer, I. Klaiber, A. Klenk, G. Nagl, H. Pöhnl, H. Sadlo, B. Vogler, Tetrahedron 1987, 43, 2817-2830.
317. For reviews on synthetic work towards azadirachtin, see: a) S. V. Ley, A. A. Denholm, A. Wood, Nat. Prod. Rep. 1993, 10, 109-157;
318. b) S. V. Ley, Pure Appl. Chem. 1994, 66, 2099-2102;
319. for our own work towards this target, see: c) K. C. Nicolaou, M. Follmann, A. J. Roecker, K. W. Hunt, Angew. Chem. 2002, 114, 2207-2210; Angew. Chem. Int. Ed. 2002, 41, 2103-2106;
320. for our own work towards this target, see: c) K. C. Nicolaou, M. Follmann, A. J. Roecker, K. W. Hunt, Angew. Chem. 2002, 114, 2207-2210; Angew. Chem. Int. Ed. 2002, 41, 2103-2106;
321. K. C. Nicolaou, A. J. Roecker, M. Follmann, R. Baati, Angew. Chem. 2002, 114, 2211-2214; Angew. Chem. Int. Ed. 2002, 41, 2107-2110;
322. K. C. Nicolaou, A. J. Roecker, M. Follmann, R. Baati, Angew. Chem. 2002, 114, 2211-2214; Angew. Chem. Int. Ed. 2002, 41, 2107-2110;
323. e) K. C. Nicolaou, A. J. Roecker, H. Monenschein, P. Guntupalli, M. Follmann, Angew. Chem. 2003, 115, 3765-3770; Angew. Chem. Int. Ed. 2003, 42, 3637-3642.
324. e) K. C. Nicolaou, A. J. Roecker, H. Monenschein, P. Guntupalli, M. Follmann, Angew. Chem. 2003, 115, 3765-3770; Angew. Chem. Int. Ed. 2003, 42, 3637-3642.
325. N. Takeuchi, T. Fujita, K. Goto, N. Morisaki, N. Osone, K. Tobinaga, Chem. Pharm. Bull. 1993, 41, 923-925.
326. D. P. Piet, R. V. A. Orru, L. H. D. Jenniskens, C. van de Haar, T. A. van Beek, M. C. R. Franssen, J. B. P. A. Wijnberg, A. de Groot, Chem. Pharm. Bull. 1996, 44, 1400-1403. Prior to the publication of this article, the isolation group had reported a total synthesis of dictamnol that verified the originally proposed structure. Their synthesis had indeed provided synthetic dictamnol, but only because their use of the strongly acidic Jones reagent caused epimerization at one bridgehead carbon atom to produce the required trans-fused hydroazulene system of the revised structure: T. Koike, K. Yamazaki, N. Fukumoto, K. Yashiro, N. Takeuchi, S. Tobinaga, Chem. Pharm. Bull. 1996, 44, 646-652.
327. D. P. Piet, R. V. A. Orru, L. H. D. Jenniskens, C. van de Haar, T. A. van Beek, M. C. R. Franssen, J. B. P. A. Wijnberg, A. de Groot, Chem. Pharm. Bull. 1996, 44, 1400-1403. Prior to the publication of this article, the isolation group had reported a total synthesis of dictamnol that verified the originally proposed structure. Their synthesis had indeed provided synthetic dictamnol, but only because their use of the strongly acidic Jones reagent caused epimerization at one bridgehead carbon atom to produce the required trans-fused hydroazulene system of the revised structure: T. Koike, K. Yamazaki, N. Fukumoto, K. Yashiro, N. Takeuchi, S. Tobinaga, Chem. Pharm. Bull. 1996, 44, 646-652.
328. For other total syntheses of dictamnol, see: a) G. L. Lange, A. Merica, M. Chimanikire, Tetrahedron Lett. 1997, 38, 6371-6374;
329. b) G. L. Lange, C. Gottardo, A. Merica, J. Org. Chem. 1999, 64, 6738-6744;
330. P. A. Wender, M. Fuji, C. O. Husfeld, J. A. Love, Org. Lett. 1999, 1, 137-139.
331. J. Chan, T. F. Jamison, J. Am. Chem. Soc. 2003, 125, 11514-11515.
332. Y. Nihashi, C.-H. Lim, C. Tanaka, H. Miyagawa, T. Ueno, Biosci. Biotechnol. Biochem. 2002, 66, 685-688.
333. a) M. Oka, S. Iimura, Y. Narita, T. Furumai, M. Konishi, T. Oki, Q. Gao, H. Kakisawa, J. Org. Chem. 1993, 58, 1875-1881;
334. b) S. Iimura, M. Oka, Y. Narita, M. Konishi, H. Kakisawa, Q. Gao, T. Oki, Tetrahedron Lett. 1993, 34, 493-496.
335. a) A. G. Myers, M. Siu, F. Ren, J. Am. Chem. Soc. 2002, 124, 4230-4232;
336. for other total syntheses of terpestacin, see: b) K. Tatsuta, N. Masuda, H. Nishida, Tetrahedron Lett. 1998, 39, 83-86;
337. K. Tatsuta; N. Masuda, J. Antibiot. 1998, 51, 602-606; the latter synthesis suffered from the same problem with the optical-rotation measurement.
338. N. Lindquist, W. Fenical, G. D. Van Duyne, J. Clardy, J. Am. Chem. Soc. 1991, 113, 2303-2304.
339. For highlights of previous synthetic studies towards the diazonamides, see: a) V. Wittmann, Nachr. Chem. 2002, 50, 477-482;
340. b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495.
341. b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495.
342. a) K. C. Nicolaou, S. A. Snyder, K. B. Simonsen, A. E. Koumbis, Angew. Chem. 2000, 112, 3615-3620; Angew. Chem. Int. Ed. 2000, 39, 3473-3478;
343. a) K. C. Nicolaou, S. A. Snyder, K. B. Simonsen, A. E. Koumbis, Angew. Chem. 2000, 112, 3615-3620; Angew. Chem. Int. Ed. 2000, 39, 3473-3478;
344. b) K. C. Nicolaou, X. Huang, N. Giuseppone, P. Bheema Rao, M. Bella, M. V. Reddy, S. A. Snyder, Angew. Chem. 2001, 113, 4841-4845; Angew. Chem. Int. Ed. 2001, 40, 4705-4709.
345. b) K. C. Nicolaou, X. Huang, N. Giuseppone, P. Bheema Rao, M. Bella, M. V. Reddy, S. A. Snyder, Angew. Chem. 2001, 113, 4841-4845; Angew. Chem. Int. Ed. 2001, 40, 4705-4709.
346. a) J. Li, S. Jeong, L. Esser, P. G. Harran, Angew. Chem. 2001, 113, 4901-4906;
347. Angew. Chem. Int. Ed. 2001, 40, 4765-4770;
348. b) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773.
349. b) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773.
350. K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S. A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499.
351. K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S. A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499.
352. K. C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
353. K. C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
354. For a review of these two syntheses, see: K. C. Nicolaou, S. A. Snyder, Classics in Total Synthesis II: More Targets, Strategies, Methods, Wiley-VCH, Weinheim, 2003, chap. 20, p. 639;
355. for the full account of our efforts towards diazonamide A, see: a) K. C. Nicolaou, S. A. Snyder, X. Huang, K. B. Simonsen, A. E. Koumbis, A. Bigot, J. Am. Chem. Soc. 2004, 126, 10162-10173;
356. b) K. C. Nicolaou, S. A. Snyder, N. Giuseppone, X. Huang, M. Bella, M. V. Reddy, P. Bheema Rao, A. E. Koumbis, P. Giannakakou, A. O'Brate, J. Am. Chem. Soc. 2004, 126, 10174-10182;
357. K. C. Nicolaou, D. Y.-K. Chen, X. Huang, T. Ling, M. Bella, S. A. Snyder, J. Am. Chem. Soc. 2004, 126, 12888-12896;
358. K. C. Nicolaou, J. Hao, M. V. Reddy, P. Bheema Rao, G. Rassias, S. A. Snyder, X. Huang, D. Y.-K. Chen, W. E. Brenzovich, N. Giuseppone, P. Giannakakou, A. O'Brate, J. Am. Chem. Soc. 2004, 126, 12897-12906.
359. A third total synthesis of diazonamide A was recently completed by the Harran group: A. W. G. Burgett, Q. Li, Q. Wei, P. G. Harran, Angew. Chem. 2003, 115, 5111-5116; Angew. Chem. Int. Ed. 2003, 42, 4961-4966.
360. A third total synthesis of diazonamide A was recently completed by the Harran group: A. W. G. Burgett, Q. Li, Q. Wei, P. G. Harran, Angew. Chem. 2003, 115, 5111-5116; Angew. Chem. Int. Ed. 2003, 42, 4961-4966.
361. K. C. Nicolaou, S. A. Snyder, A. Bigot, J. A. Pfefferkorn, Angew. Chem. 2000, 112, 1135-1138; Angew. Chem. Int. Ed. 2000, 59, 1093-1096.
362. K. C. Nicolaou, S. A. Snyder, A. Bigot, J. A. Pfefferkorn, Angew. Chem. 2000, 112, 1135-1138; Angew. Chem. Int. Ed. 2000, 59, 1093-1096.
363. K. C. Nicolaou, A. E. Koumbis, S. A. Snyder, K. B. Simonsen, Angew. Chem. 2000, 112, 2629-2633;
364. Angew. Chem. Int. Ed. 2000, 59, 2529-2533.
365. a) K. C. Nicolaou, X. Huang, S. A. Snyder, P. Bheema Rao, M. Bella, M. V. Reddy, Angew. Chem. 2002, 114, 862-866; Angew. Chem. Int. Ed. 2002, 41, 834-838;
366. a) K. C. Nicolaou, X. Huang, S. A. Snyder, P. Bheema Rao, M. Bella, M. V. Reddy, Angew. Chem. 2002, 114, 862-866; Angew. Chem. Int. Ed. 2002, 41, 834-838;
367. b) K. C. Nicolaou, D. A. Longbottom, S. A. Snyder, A. Z. Nalbandian, X. Huang, Angew. Chem. 2002, 114, 4022-4026; Angew. Chem. Int. Ed. 2002, 41, 3866-3870;
368. b) K. C. Nicolaou, D. A. Longbottom, S. A. Snyder, A. Z. Nalbandian, X. Huang, Angew. Chem. 2002, 114, 4022-4026; Angew. Chem. Int. Ed. 2002, 41, 3866-3870;
369. K. C. Nicolaou, S. A. Snyder, A. Z. Nalbandian, D. A. Longbottom, J. Am. Chem. Soc. 2004, 126, 6234-6235;
370. for the full account of this work, see: d) K. C. Nicolaou, S. A. Snyder, D. A. Longbottom, A. Z. Nalbandian, X. Huang, Chem. Eur. J. 2004, 10, 5581-5606.
371. M. Satake, K. Ofuji, H. Naoki, K. J. James, A. Furey, T. McMahon, J. Silke, T. Yasumoto, J. Am. Chem. Soc. 1998, 120, 9967-9968; for the later isolation of some structurally related compounds, see: K. Ofuji, M. Satake, T. McMahon, K. J. James, H. Naoki, Y. Oshima, T. Yasumoto, Biosci. Biotechnol. Biochem. 2001, 65, 740-742.
372. M. Satake, K. Ofuji, H. Naoki, K. J. James, A. Furey, T. McMahon, J. Silke, T. Yasumoto, J. Am. Chem. Soc. 1998, 120, 9967-9968; for the later isolation of some structurally related compounds, see: K. Ofuji, M. Satake, T. McMahon, K. J. James, H. Naoki, Y. Oshima, T. Yasumoto, Biosci. Biotechnol. Biochem. 2001, 65, 740-742.
373. a) R. G. Carter, D. J. Weldon, Org. Lett. 2000, 2, 3913-3916;
374. b) J. Aiguade, J. Hao, C. J. Forsyth, Tetrahedron Lett. 2001, 42, 817-820;
375. J. Hao, J. Aiguade, C. J. Forsyth, Tetrahedron Lett. 2001, 42, 821-824;
376. A. B. Dounay, C. J. Forsyth, Org. Lett. 2001, 3, 975-978;
377. e) J. Aiguade, J. Hao, C. J. Forsyth, Org. Lett. 2001, 3, 979-982:
378. f) C. J. Forsyth, J. Hao, J. Aiguade, Angew. Chem. 2001, 113, 3775-3779; Angew. Chem. Int. Ed. 2001, 40, 3663-3667.
379. f) C. J. Forsyth, J. Hao, J. Aiguade, Angew. Chem. 2001, 113, 3775-3779; Angew. Chem. Int. Ed. 2001, 40, 3663-3667.
380. a) K. C. Nicolaou, P. M. Pihko, N. Diedrichs, N. Zou, F. Bernal, Angew. Chem. 2001, 113, 1302-1305; Angew. Chem. Int. Ed. 2001, 40, 1262-1265;
381. a) K. C. Nicolaou, P. M. Pihko, N. Diedrichs, N. Zou, F. Bernal, Angew. Chem. 2001, 113, 1302-1305; Angew. Chem. Int. Ed. 2001, 40, 1262-1265;
382. b) K. C. Nicolaou, W. Qian, F. Bernal, N. Uesaka, P. M. Pihko, J. Hinrichs, Angew. Chem. 2001, 113, 3775-3779; Angew. Chem. Int. Ed. 2001, 40, 4068-4071.
383. b) K. C. Nicolaou, W. Qian, F. Bernal, N. Uesaka, P. M. Pihko, J. Hinrichs, Angew. Chem. 2001, 113, 3775-3779; Angew. Chem. Int. Ed. 2001, 40, 4068-4071.
384. a) K. C. Nicolaou, Y. Li, N. Uesaka, T. V. Koftis, S. Vyskocil, T. Ling, M. Govindasamy, W. Qian, F. Bernal, D. Y.-K. Chen, Angew. Chem. 2003, 115, 3771-3776; Angew. Chem. Int. Ed. 2003, 42, 3643-3648;
385. a) K. C. Nicolaou, Y. Li, N. Uesaka, T. V. Koftis, S. Vyskocil, T. Ling, M. Govindasamy, W. Qian, F. Bernal, D. Y.-K. Chen, Angew. Chem. 2003, 115, 3771-3776; Angew. Chem. Int. Ed. 2003, 42, 3643-3648;
386. b) K. C. Nicolaou, D. Y.-K. Chen, Y. Li, W. Qian, T. Ling, S. Vyskocil, T. V. Koftis, M. Govindasamy, N. Uesaka, Angew. Chem. 2003, 115, 3777-3781; Angew. Chem. Int. Ed. 2003, 42, 3649-3653.
387. b) K. C. Nicolaou, D. Y.-K. Chen, Y. Li, W. Qian, T. Ling, S. Vyskocil, T. V. Koftis, M. Govindasamy, N. Uesaka, Angew. Chem. 2003, 115, 3777-3781; Angew. Chem. Int. Ed. 2003, 42, 3649-3653.
388. a) K. C. Nicolaou, S. Vyskocil, T. V. Koftis, Y M. A. Yamada, T. Ling, D. Y.-K. Chen, W. Tang, G. Petrovic, M. Frederick, Y. Li, M. Satake, Angew. Chem. 2004, 116, 4412-4418; Angew. Chem. Int. Ed. 2004, 43, 4312-4318;
389. a) K. C. Nicolaou, S. Vyskocil, T. V. Koftis, Y M. A. Yamada, T. Ling, D. Y.-K. Chen, W. Tang, G. Petrovic, M. Frederick, Y. Li, M. Satake, Angew. Chem. 2004, 116, 4412-4418; Angew. Chem. Int. Ed. 2004, 43, 4312-4318;
390. b) K. C. Nicolaou, T. V. Koftis, S. Vyskocil, G. Petrovic, T. Ling, Y. M. A. Yamada, T. Ling, W. Tang, M. Frederick, Angew. Chem. 2004, 116, 4418-4424; Angew. Chem. Int. Ed. 2004, 45, 4318-4324.
391. b) K. C. Nicolaou, T. V. Koftis, S. Vyskocil, G. Petrovic, T. Ling, Y. M. A. Yamada, T. Ling, W. Tang, M. Frederick, Angew. Chem. 2004, 116, 4418-4424; Angew. Chem. Int. Ed. 2004, 45, 4318-4324.
392. C. Hopmann, D. J. Faulkner, Tetrahedron Lett. 1997, 38, 169-170.
393. For a recent review on the types of discoveries that can emanate from programs in total synthesis, see: K. C. Nicolaou, S. A. Snyder, Proc. Natl. Acad. Sci. USA, 2004, 101, 11929-11936.
394. Note added in proof (17 January 2005): Since the submission of this Review, a number of additional structural revisions of natural products have been reported. Most involve stereochemical misassignments, but several are more profound. Rather than cite these works (as there are many), we suggest using a search engine such as SciFinder with terms such as "misassigned structure", "revised structure", and "structural revision" if you wish to explore this area further. Should a future review on this subject appear from other authors, hopefully these examples, as well as others not expounded upon here, will be presented in more detail.