Metathesis reactions in total synthesis

Angewandte Chemie - International Edition

Volumn 44, Issue 29, 2005, Pages 4490-4527

  Nicolaou, K C ^a,b   Bulger, Paul G ^a,b   Sarlah, David ^a,b,c,d  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

^b UNIVERSITY OF CALIFORNIA   (United States)

^c UNIVERSITY OF LJUBLJANA   (Slovenia)

^d NATIONAL INSTITUTE OF CHEMISTRY   (Slovenia)

Author keywords

Alkene metathesis; Alkyne metathesis; Enyne metathesis; Natural products; Total synthesis

Indexed keywords

CARBON; CATALYSTS; OLEFINS; PALLADIUM COMPOUNDS;

ALKYNES; CARBON-CARBON BOUNDS; METATHESIS REACTIONS; PALLADIUM-CATALYZED CROSS-COUPLING;

SYNTHESIS (CHEMICAL);

ALKENE; ALKYNE; CARBON; ORGANOMETALLIC COMPOUND; PALLADIUM;

ALKYLATION; CATALYSIS; CHEMICAL MODEL; CHEMISTRY; CYCLIZATION; METHODOLOGY; ORGANIC CHEMISTRY; REVIEW; STEREOISOMERISM; SYNTHESIS;

ALKENES; ALKYLATION; ALKYNES; CARBON; CATALYSIS; CHEMISTRY, ORGANIC; CYCLIZATION; MODELS, CHEMICAL; ORGANOMETALLIC COMPOUNDS; PALLADIUM; STEREOISOMERISM;

EID: 22744448499     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200500369     Document Type: Review

References (430)

1. Grignard Reagents: New Developments (Ed.: H. G. Richey), Wiley, Chichester, 2000, p. 418.
2. For an overview of the utility of the Diels-Alder reaction in total synthesis, see: K. C. Nicolaou, S. A. Snyder, T. Montagnon, G. Vassilikogiannakis, Angew. Chem. 2002, 114, 1742-1773;
3. Angew. Chem. Int. Ed. 2002, 41, 1668-1698.
4. K. C. Nicolaou, M. W. Härter, J. L. Gunzner, A. Nadin, Liebigs Ann./Recl. 1997, 1283-1301.
5. K. C. Nicolaou, P. G. Bulger, D. Sarlah, Angew. Chem. 2005, 117, 4516-4563,
6. Angew. Chem. Int. Ed. 2005, 44, 4442-4489, preceding Review article in this issue.
7. For a comprehensive treatise of metathesis reactions and applications, see: Handbook of Metathesis, Vols. 1, 2, 3 (Ed.: R. H. Grubbs), Wiley-VCH, Weinheim, 2003, p. 1234.
8. For reviews of the alkene-metathesis reaction, see: a) B. Schmidt, J. Hermanns, Top. Organomet. Chem. 2004, 7, 223-267;
9. b) S. J. Connon, S. Blechert, Top. Organomet. Chem. 2004, 7, 93-124;
10. c) A. Fürstner, Angew. Chem. 2000, 112, 3140-3172;
11. Angew. Chem. Int. Ed. 2000, 39, 3012-3043;
12. d) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413-4450;
13. for a review of olefin and enyne metathesis, see: J. Prunet, L. Grimauld, Comprehensive Organic Functional Group Transformations II, Vol. 1 (Eds.: A. R. Katritzky, R. J. K. Taylor), Elsevier, Oxford, 2005, pp. 669-722.
14. a) K. J. Ivin, J. C. Mol, Olefin Metathesis and Metathesis Polymerization, Academic Press, San Diego, 1997, p. 496;
15. b) K. C. Nicolaou, S. A. Snyder, Classics in Total Synthesis II, Wiley-VCH, Weinheim, 2003, pp. 166-172;
16. c) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18-29.
17. J.-L. Hérisson, Y. Chauvin, Makromol. Chem. 1971, 141, 161-176.
18. C. P. Casey, T. J. Burkhardt, J. Am. Chem. Soc. 1974, 96, 7808-7809.
19. T. J. Katz, J. McGinnis, J. Am. Chem. Soc. 1975, 97, 1592-1594.
20. a) R. H. Grubbs, P. L. Burk, D. D. Carr, J. Am. Chem. Soc. 1975, 97, 3265-3267;
21. b) R. H. Grubbs, D. D. Carr, C. Hoppin, P. L. Burk, J. Am. Chem. Soc. 1976, 98, 3478-3483.
22. a) J. McGinnis, T. J. Katz, S. Hurwitz, J. Am. Chem. Soc. 1976, 98, 605-606;
23. b) T. J. Katz, J. McGinnis, C. Altus, J. Am. Chem. Soc. 1976, 98, 606-608;
24. c) T. J. Katz, S. J. Lee, N. Acton, Tetrahedron Lett. 1976, 17, 4247-4250;
25. d) T. J. Katz, N. Acton, Tetrahedron Lett. 1976, 17, 4251-4254;
26. e) S. J. Lee, J. McGinnis, T. J. Katz, J. Am. Chem. Soc. 1976, 98, 7818-7819.
27. T. J. Katz, Angew. Chem. 2005, 117, 3070-3079;
28. Angew. Chem. Int. Ed. 2005, 44, 3010-3019.
29. For specific reviews of the enyne-metathesis reaction, see: a) S. T. Diver, A. J. Giessert, Chem. Rev. 2004, 104, 1317-1382;
30. b) C. S. Poulsen, R. Madsen, Synthesis 2003, 1-18;
31. c) M. Mori, Top. Organomet. Chem. 1998, 1, 133-154.
32. B. M. Trost, Acc. Chem. Res. 2002, 35, 695-705.
33. T. J. Katz, T. M. Sivavec, J. Am. Chem. Soc. 1985, 107, 737-738.
34. a) B. M. Trost, G. J. Tanoury, J. Am. Chem. Soc. 1988, 110, 1636-1638;
35. b) B. M. Trost, V. K. Chang, Synthesis 1993, 824-832.
36. More recently, analogous gallium(III)-catalyzed skeletal reorganizations of enynes have been reported: N. Chatani, H. Inoue, T. Kotsuma, S. Murai, J. Am. Chem. Soc. 2002, 124, 10 294-10 295.
37. C. Aubert, O. Buisine, M. Malacria, Chem. Rev. 2002, 102, 813-814.
38. For a review of transition-metal-catalyzed cycloisomerizations, see: B. M. Trost, M. J. Krische, Synlett 1998, 1-18.
39. N. Chatani, T. Morimoto, T. Muto, S. Murai, J. Am. Chem. Soc. 1994, 116, 6049-6050.
40. N. Chatani, H. Inoue, T. Morimoto, T. Muto, S. Murai, J. Org. Chem. 2001, 66, 4433-4436.
41. a) N. Chatani, N. Furukawa, H. Sakurai, S. Murai, Organometallics 1996, 15, 901-903;
42. b) A. Fürstner, F. Stelzer, H. Szillat, J. Am. Chem. Soc. 2001, 123, 11 863-11 869.
43. For specific reviews of the alkyne-metathesis reaction, see: a) A. Fürstner, P. W. Davies, Chem. Commun. 2005, 2307-2320;
44. b) T. Lindel in Organic Synthesis Highlights V (Eds.: H.-G. Schmalz, T. Wirth), Wiley-VCH, Weinheim, 2003, pp. 27-35;
45. c) U. H. F. Bunz, L. Kloppenburg, Angew. Chem. 1999, 111, 503-505;
46. Angew. Chem. Int. Ed. 1999, 38, 478-481.
47. A. Mortreux, M. Blanchard, J. Chem. Soc. Chem. Commun. 1974, 786-787.
48. Heterogeneous catalysis of alkyne metathesis (at temperatures between 200 and 450°C) had been documented earlier: F. Pennella, R. L. Banks, G. C. Bailey, J. Chem. Soc. Chem. Commun. 1968, 1548-1549.
49. J. Mulzer, E. Öhler, Top. Organomet. Chem. 2004, 7, 269-366.
50. R. R. Schrock, J. S. Murdzek, G. C. Bazan, J. Robbins, M. DiMare, M. O'Regan, J. Am. Chem. Soc. 1990, 112, 3875-3886.
51. For reviews of the use of molybdenum imido alkylidene catalysts in alkene metathesis, see: a) R. R. Schrock, A. H. Hoveyda, Angew. Chem. 2003, 115, 4740-4782;
52. Angew. Chem. Int. Ed. 2003, 42, 4592-4633;
53. b) R. R. Schrock, Tetrahedron 1999, 55, 8141-8153;
54. c) R. R. Schrock, Top. Organomet. Chem. 1998, 1, 1-36.
55. A well-defined rhenium(VII) alkene-metathesis catalyst was also developed by the Schrock group, but has not found widespread use: R. Toreki, R. R. Schrock, J. Am. Chem. Soc. 1990, 112, 2448-2449.
56. S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1992, 114, 3974-3975.
57. a) P. Schwab, M. B. France, J. W. Ziller, R. H. Grubbs, Angew. Chem. 1995, 107, 2179-2181;
58. Angew. Chem. Int. Ed. Engl. 1995, 34, 2039-2041;
59. b) P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1996, 118, 100-110.
60. For reviews of the utility of N-heterocyclic carbene ligands in transition-metal catalysis, see: a) W. A. Herrmann, Angew. Chem. 2002, 114, 1342-1363;
61. Angew. Chem. Int. Ed. 2002, 41, 1290-1309;
62. b) W. A. Herrmann, C. Köcher, Angew. Chem. 1997, 109, 2257-2282;
63. Angew. Chem. Int. Ed. Engl. 1997, 36, 2162-2187.
64. a) T. Weskamp, F. J. Kohl, W. Hieringer, D. Gleich, W. A. Herrmann, Angew. Chem. 1999, 111, 2573-2576;
65. Angew. Chem. Int. Ed. 1999, 38, 2416-2419;
66. b) M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247-2250;
67. c) J. Huang, E. D. Stevens, S. P. Nolan, J. L. Petersen, J. Am. Chem. Soc. 1999, 121, 2674-2678;
68. d) J. Huang, H.-J. Schanz, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 5375-5380;
69. e) L. Ackermann, A. Fürstner, T. Weskamp, F. J. Kohl, W. A. Herrmann, Tetrahedron Lett. 1999, 40, 4787-4790.
70. These studies had been preceded by a pioneering report by the Herrmann group in which both phosphine ligands in the first-generation ruthenium complex were replaced with N-heterocyclic carbene ligands: T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Herrmann, Angew. Chem. 1998, 110, 2631-2633;
71. Angew. Chem. Int. Ed. 1998, 37, 2490-2493.
72. M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953-956.
73. For examples of the development of novel catalysts for metathesis, see: a) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 2509-2511;
74. Angew. Chem. Int. Ed. 2002, 41, 2403-2405;
75. b) S. J. Connon, A. M. Dunne, S. Blechert, Angew. Chem. 2002, 114, 3989-3993;
76. Angew. Chem. Int. Ed. 2002, 41, 3835-3838;
77. c) J. J. Van Veldhuizen, S. B. Garber, J. S. Kingsbury, A. H. Hoveyda, J. Am. Chem. Soc. 2002, 124, 4954-4955;
78. d) A. Fürstner, L. Ackermann, B. Gabor, R. Goddard, C. W. Lehmann, R. Mynott, F. Stelzer, O. R. Thiel, Chem. Eur. J. 2001, 7, 3236-3253.
79. For a review of the synthesis of oxygen- and nitrogen-containing heterocycles by ring-closing metathesis, see: a) A. Deiters, S. F. Martin, Chem. Rev. 2004, 104, 2199-2238;
80. for a review of the synthesis of phosphorus- and sulfur-containing heterocycles by ring-closing metathesis, see: b) M. D. McReynolds, J. M. Dougherty, P. R. Hanson, Chem. Rev. 2004, 104, 2239-2258;
81. for a review of total syntheses of piperidine and pyrrolidine alkaloids with ring-closing metathesis as a key step, see: c) F.-X. Felpin, J. Lebreton, Eur. J. Org. Chem. 2003, 3693-3712.
82. K. C. Nicolaou, R. M. Rodríguez, H. J. Mitchell, F. L. van Delft, Angew. Chem. 1998, 110, 1975-1977;
83. Angew. Chem. Int. Ed. 1998, 37, 1874-1876.
84. For a review of the applications of alkene metathesis and related reactions in carbohydrate chemistry, see: R. Roy, S. K. Das, Chem. Commun. 2000, 519-529.
85. For the total synthesis of this complex oligosaccharide, see: a) K. C. Nicolaou, H. J. Mitchell, H. Suzuki, R. M. Rodriguez, O. Baudoin, K. C. Fylatakidou, Angew. Chem. 1999, 111, 3523-3528;
86. Angew. Chem. Int. Ed. 1999, 38, 3334-3339;
87. b) K. C. Nicolaou, R. M. Rodríguez, K. C. Fylaktakidou, H. Suzuki, H. J. Mitchell, Angew. Chem. 1999, 111, 3529-3534;
88. Angew. Chem. Int. Ed. 1999, 38, 3340-3345;
89. c) K. C. Nicolaou, H. J. Mitchell, R. M. Rodríguez, K. C. Fylaktakidou, H. Suzuki, Angew. Chem. 1999, 111, 3535-3540;
90. Angew. Chem. Int. Ed. 1999, 38, 3345-3350;
91. d) K. C. Nicolaou, R. M. Rodríguez, H. J. Mitchell, H. Suzuki, K. C. Fylaktakidou, O. Baudoin, F. L. van Delft, Chem. Eur. J. 2000, 6, 3095-3115;
92. e) K. C. Nicolaou, H. J. Mitchell, K. C. Fylaktakidou, R. M. Rodríguez, H. Suzuki, Chem. Eur. J. 2000, 6, 3116-3148;
93. f) K. C. Nicolaou, H. J. Mitchell, R. M. Rodríguez, K. C. Fylaktakidou, H. Suzuki, S. R. Conley, Chem. Eur. J. 2000, 6, 3149-3165.
94. A. Nickel, T. Maruyama, H. Tang, P. D. Murphy, B. Greene, N. Yusuff, J. L. Wood, J. Am. Chem. Soc. 2004, 126, 16 300-16 301.
95. S. Kim, J. Winkler, Chem. Soc. Rev. 1997, 26, 387-399.
96. M. Blanco-Molina, G. C. Tron, A. Macho, C. Lucena, M. A. Calzado, E. Muñoz, G. Appendino, Chem. Biol. 2001, 8, 767-778, and references therein.
97. For a review of inside-outside isomerism, see: R. W. Alder, S. P. East, Chem. Rev. 1992, 92, 2097-2111.
98. For the successful construction of this bridgehead junction with the correct stereochemistry, see: a) J. H. Rigby, B. Bazin, J. H. Meyer, F. Mohammadi, Org. Lett. 2002, 4, 799-801;
99. b) R. L. Funk, T. A. Olmstead, M. Parvez, J. B. Stallman, J. Am. Chem. Soc. 1993, 115, 5873-5875.
100. For other total syntheses of ingenol, see: a) K. Tanino, K. Onuki, K. Asano, M. Miyashita, T. Nakamura, Y. Takahashi, I. Kuwajima, J. Am. Chem. Soc. 2003, 125, 1498-1500;
101. b) J. D. Winkler, M. B. Rouse, M. F. Greaney, S. J. Harrison, Y. T. Jeon, J. Am. Chem. Soc. 2002, 124, 9726-9728;
102. for a formal total synthesis, see: c) K. Watanabe, Y. Suzuki, K. Aoki, A. Sakakura, K. Suenaga, H. Kigoshi, J. Org. Chem. 2004, 69, 7802-7808.
103. It is worth recalling that ring-opening-metathesis polymerization reactions are widely used in the industrial production of polymers of great commercial value. For examples, see: M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124-2145;
104. Angew. Chem. Int. Ed. Engl. 1997, 36, 2036-2056, and references therein.
105. H. Tang, N. Yusuff, J. L. Wood, Org. Lett. 2001, 3, 1563-1566.
106. A related metathesis-based approach to the ingenol ABC-ring core structure has also been reported: H. Kigoshi, Y. Suzuki, K. Aoki, D. Uemura, Tetrahedron Lett. 2000, 41, 3927-3930.
107. S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 8168-8179.
108. S. Gessler, S. Randl, S. Blechert, Tetrahedron Lett. 2000, 41, 9973-9976.
109. For a very recent approach to the "inside-outside" tetracyclic core structure of ingenol employing ring-closing metathesis, see: O. L. Epstein, J. K. Cha, Angew. Chem. 2005, 117, 123-125;
110. Angew. Chem. Int. Ed. 2005, 44, 121-123.
111. P. A. Evans, J. Cui, S. J. Gharpure, A. Polosukhin, H.-R. Zhang, J. Am. Chem. Soc. 2003, 125, 14 702-14 703.
112. For reviews of the utility of temporary silicon tethers in organic synthesis, see: a) L. Fensterbank, M. Malacria, S. M. Sieburth, Synthesis 1997, 813-854;
113. b) M. Bols, T. Skrydstrup, Chem. Rev. 1995, 95, 1253-1277.
114. The first application of a silicon-tethered ring-closing-metathesis reaction in a total synthesis had been disclosed the previous year by the Eustache group, in their elegant synthesis of attenol A: P. Van de Weghe, D. Aoun, J.-G. Boiteau, J. Eustache, Org. Lett. 2002, 4, 4105-4108.
115. For other examples of silicon-tethered ring-closing-metathesis reactions, see: a) B. A. Harrison, G. L. Verdine, Org. Lett. 2001, 3, 2157-2159;
116. b) S. E. Denmark, S.-M. Yang, Org. Lett. 2001, 3, 1749-1752;
117. c) T. M. Gerash, M. Chytil, M. T. Didiuk, J. Y. Park, J. J. Urban, S. P. Nolan, G. L. Verdine, Org. Lett. 2000, 2, 3999-4000;
118. d) A. Briot, M. Bujard, V. Gouverneur, S. P. Nolan, C. Mioskowski, Org. Lett. 2000, 2, 1517-1519;
119. e) T. R. Hoye, M. A. Promo, Tetrahedron Lett. 1999, 40, 1429-1432;
120. f) P. A. Evans, V. S. Murthy, J. Org. Chem. 1998, 63, 6768-6769;
121. g) G. C. Fu, R. H. Grubbs, J. Am. Chem. Soc. 1992, 114, 7324-7325.
122. P. A. Evans, J. Cui, G. P. Buffone, Angew. Chem. 2003, 115, 1776-1779;
123. Angew. Chem. Int. Ed. 2003, 42, 1734-1737.
124. For other total syntheses of mucocin, see: a) S. Takahashi, A. Kubota, T. Nakata, Angew. Chem. 2002, 114, 4945-4948;
125. Angew. Chem. Int. Ed. 2002, 41, 4751-4754;
126. b) S. Takahashi, T. Nakata, J. Org. Chem. 2002, 67, 5739-5752;
127. c) S. Bäurle, S. Hoppen, U. Koert, Angew. Chem. 1999, 111, 1341-1344;
128. Angew. Chem. Int. Ed. 1999, 38, 1263-1266;
129. d) P. Neogi, T. Doundoulakis, A. Yazbak, S. C. Sinha, S. C. Sinha, E. Keinan, J. Am. Chem. Soc. 1998, 120, 11 279-11 284.
130. Another temporary tether that has found use in ring-closing-metathesis applications is the ester linkage; for an example, see: G. L. Nattrass, E. Diez, M. M. McLachlan, D. J. Dixon, S. V. Ley, Angew. Chem. 2005, 117, 586-590;
131. Angew. Chem. Int. Ed. 2005, 44, 580-584.
132. For a Review of the synthesis of medium-sized rings by the ring-closing-metathesis reaction, see: M. E. Maier, Angew. Chem. 2000, 112, 2153-2157;
133. Angew. Chem. Int. Ed. 2000, 39, 2073-2076.
134. a) K. C. Nicolaou, G. Vassilikogiannakis, T. Montagnon, Angew. Chem. 2002, 114, 3410-3415;
135. Angew. Chem. Int. Ed. 2002, 41, 3276-3281;
136. b) G. Vassilikogiannakis, I. Margaros, M. Tofi, Org. Lett. 2004, 6, 205-208;
137. c) K. C. Nicolaou, T. Montagnon, G. Vassilikogiannakis, C. J. N. Mathison, J. Am. Chem. Soc. 2005, 127, 8872-8888.
138. A number of other ingenious concepts for controlling the stereochemical course of ring-closing-metathesis reactions to generate medium-sized ring systems have been developed; for selected examples, see: a) A. Fürstner, K. Radkowski, C. Wirtz, R. Goddard, C. W. Lehmann, R. Mynott, J. Am. Chem. Soc. 2002, 124, 7061-7069 (selective formation of either the E or Z isomer by exerting either kinetic or thermodynamic control, respectively, in the ring-closing-metathesis event);
139. b) A. Ivkovic, R. Matovic, R. N. Saicic, Org. Lett. 2004, 6, 1221-1224 (a ring-closing-metathesis/Grob fragmentation strategy to afford Z-configured medium-sized cycloalkenes);
140. c) E. A. Couladouros, A. P. Mihou, E. A. Bouzas, Org. Lett. 2004, 6, 977-980 (control of metathesis precursor conformation through the presence or absence of intramolecular hydrogen bonding, leading to Z- or E-configured cycloalkenes, respectively).
141. a) M. Inoue, K. Miyazaki, H. Uehara, M. Maruyama, M. Hirama, Proc. Natl. Acad. Sci. USA 2004, 101, 12 013-12 018;
142. b) M. Inoue, H. Uehara, M. Maruyama, M. Hirama, Org. Lett. 2002, 4, 4551-4554;
143. c) M. Hirama, T. Oishi, H. Uehara, M. Inoue, M. Maruyama, H. Oguri, M. Satake, Science 2001, 294, 1904-1907.
144. Z. Xu, C. W. Johnson, S. S. Salman, A. H. Hoveyda, J. Am. Chem. Soc. 1996, 118, 10 926-10 927.
145. For a discussion of the parameters required for successful macrocyclization, see: A. Fürstner, G. Siedel, N. Kindler, Tetrahedron 1999, 55, 8215-8230.
146. For a discussion of the chemistry, biology, and medicine of the epothilones, see: K. C. Nicolaou, A. Ritzén, K. Namoto, Chem. Commun. 2001, 1523-1535, and references therein.
147. a) Z. Yang, Y. He, D. Vourloumis, H. Vallberg, K. C. Nicolaou, Angew. Chem. 1997, 109, 170-173;
148. Angew. Chem. Int. Ed. Engl. 1997, 36, 166-168;
149. b) K. C. Nicolaou, Y. He, D. Vourloumis, H. Vallberg, F. Roschangar, F. Sarabia, S. Ninkovic, Z. Yang, J. I. Trujillo, J. Am. Chem. Soc. 1997, 119, 7960-7973.
150. D. Meng, P. Bertinato, A. Balog, D.-S. Su, T. Kamenecka, E. J. Sorensen, S. J. Danishefsky, J. Am. Chem. Soc. 1997, 119, 10 073-11 092.
151. The Danishefsky group had previously reported the first total synthesis of epothilone C, in which they employed a non-metathesis-based approach: A. Balog, D. Meng, T. Kamenecka, P. Bertinato, D.-S. Su, E. J. Sorensen, S. J. Danishefsky, Angew. Chem. 1996, 108, 2976-2978;
152. Angew. Chem. Int. Ed. Engl. 1996, 35, 2801-2803.
153. a) D. Schinzer, A. Limberg, A. Bauer, O. M. Böhm, M. Cordes, Angew. Chem. 1997, 109, 543-544;
154. Angew. Chem. Int. Ed. Engl. 1997, 36, 523-524;
155. b) D. Schinzer, A. Bauer, O. M. Böhm, A. Limberg, M. Cordes, Chem. Eur. J. 1999, 5, 2483-2491.
156. For examples of variations in EIZ selectivity, see: J. Prunet, Angew. Chem. 2003, 115, 2932-2936;
157. Angew. Chem. Int. Ed. 2003, 42, 2826-2830, and references therein.
158. For examples and a discussion of this concept, see: A. Fürstner, T. Dierkes, O. R. Thiel, G. Blanda, Chem. Eur. J. 2001, 7, 5286-5298, and references therein.
159. For general discussions of this topic, see: Handbook of Combinatorial Chemistry: Drugs, Catalysts, Methods, Vols. 1,2 (Eds.: K. C. Nicolaou, R. Hanko, W. Hartwig), Wiley-VCH, Weinheim, 2002, p. 1114.
160. For a discussion of the concepts of ring-closing metathesis applied to polymer-bound substrates, see: J.-U. Peters, S. Blechert, Synlett 1997, 348-350.
161. a) K. C. Nicolaou, N. Winssinger, J. Pastor, S. Ninkovic, F. Sarabia, Y. He, D. Vourloumis, Z. Yang, T. Li, P. Giannakakou, E. Hamel, Nature 1997, 387, 268-272;
162. b) K. C. Nicolaou, D. Vourloumis, T. Li, J. Pastor, N. Winssinger, Y. He, S. Ninkovic, F. Sarabia, H. Vallberg, F. Roschangar, N. P. King, M. R. V. Finlay, P. Giannakakou, P. Verdier-Pinard, E. Hamel, Angew. Chem. 1997, 109, 2181-2187;
163. Angew. Chem. Int. Ed. Engl. 1997, 36, 2097-2103.
164. R. E. Maleczka, Jr., L. R. Terrell, F. Geng, J. S. Ward III, Org. Lett. 2002, 4, 2841-2844.
165. A similar observation has been reported: T. R. Hoye, H. Zhao, Org. Lett. 1999, 1, 1123-1125.
166. The originally proposed structure of amphidinolide A was also synthesized by the Pattenden and Trost groups at around the same time; both groups confirmed that it did not correspond to the natural product: a) H. W. Lam, G. Pattenden, Angew. Chem. 2002, 114, 526-529;
167. Angew. Chem. Int. Ed. 2002, 41, 508-511;
168. b) B. M. Trost, J. D. Chisholm, S. A. Wrobleski, M. Jung, J. Am. Chem. Soc. 2002, 124, 12 420-12 421.
169. B. M. Trost, P. E. Harrington, J. Am. Chem. Soc. 2004, 126, 5028-5029.
170. For examples of the use of metathesis reactions in the total synthesis of other members of the amphidinolide family of natural products, see: a) A. K. Ghosh, G. Gong, J. Am. Chem. Soc. 2004, 126, 3704-3705;
171. b) C. Aïssa, R. Riveiros, J. Ragot, A. Fürstner, J. Am. Chem. Soc. 2003, 125, 15 512-15 520;
172. c) A. K. Ghosh, C. Liu, J. Am. Chem. Soc. 2003, 125, 2374-2375;
173. d) A. Fürstner, C. Aïssa, R. Riveiros, J. Ragot, Angew. Chem. 2002, 114, 4958-4960;
174. Angew. Chem. Int. Ed. 2002, 41, 4763-4766.
175. a) A. Fürstner, F. Jeanjean, P. Razon, Angew. Chem. 2002, 114, 2203-2206;
176. Angew. Chem. Int. Ed. 2002, 41, 2097-2101;
177. b) A. Fürstner, F. Jeanjean, P. Razon, C. Wirtz, R. Mynott, Chem. Eur. J. 2003, 9, 307-319;
178. c) A. Fürstner, F. Jeanjean, P. Razon, C. Wirtz, R. Mynott, Chem. Eur. J. 2003, 9, 320-326.
179. For a review of the total synthesis and biological evaluation of macrocyclic glycolipids, see: A. Fürstner, Eur. J. Org. Chem. 2004, 943-958.
180. S. Barluenga, P. Lopez, E. Moulin, N. Winssinger, Angew. Chem. 2004, 116, 3549-3552;
181. Angew. Chem. Int. Ed. 2004, 43, 3467-3470.
182. Analogous ring-closing-metathesis approaches to the synthesis of the structurally related natural product radicicol had been documented: a) R. M. Garbaccio, S. J. Stachel, D. K. Baeschlin, S. J. Danishefsky, J. Am. Chem. Soc. 2001, 123, 10 903-10 908;
183. b) Z.-Q. Yang, S. J. Danishefsky, J. Am. Chem. Soc. 2003, 125, 9602-9603.
184. For examples of this general phenomenon of regioselectivity on the ring-closing-metathesis reactions of diene-ene systems, see: L. A. Paquette, K. Basu, J. C. Eppich, J. E. Hofferberth, Helv. Chim. Acta 2002, 85, 3033-3051.
185. K. Yamamoto, K. Biswas, C. Gaul, S. J. Danishefsky, Tetrahedron Lett. 2003, 44, 3297-3299.
186. For an excellent review of the principles and practice of relay ring-closing metathesis, see: D. J. Wallace, Angew. Chem. 2005, 117, 1946-1949;
187. Angew. Chem. Int. Ed. 2005, 44, 1912-1915.
188. X. Wang, E. J. Bowman, B. J. Bowman, J. A. Porco, Jr., Angew. Chem. 2004, 116, 3685-3689;
189. Angew. Chem. Int. Ed. 2004, 43, 3601-3605.
190. T. R. Hoye, C. S. Jeffrey, M. A. Tennakoon, J. Wang, H. Zhao, J. Am. Chem. Soc. 2004, 126, 10210-10211.
191. For selected additional examples of diene-ene-metathesis reactions in natural product synthesis, see: a) G. Evano, J. V. Schaus, J. S. Panek, Org. Lett. 2004, 6, 525-528;
192. b) K. Biswas, H. Lin, J. T. Njardarson, M. D. Chappell, T.-C. Chou, Y. Guan, W. P. Tong, L. He, S. B. Horwitz, S. J. Danishefsky, J. Am. Chem. Soc. 2002, 124, 9825-9832;
193. c) C. A. Dvorak, W. D. Schmitz, D. J. Poon, D. C. Pryde, J. P. Lawson, R. A. Amos, A. I. Meyers, Angew. Chem. 2000, 112, 1730-1732;
194. Angew. Chem. Int. Ed. 2000, 39, 1664-1666.
195. For reviews of alkene cross-metathesis, see: a) S. J. Connon, S. Blechert, Angew. Chem. 2003, 115, 1944-1968;
196. Angew. Chem. Int. Ed. 2003, 42, 1900-1923;
197. b) S. E. Gibson, S. P. Keen, Top. Organomet. Chem. 1998, 1, 155-181.
198. a) A. K. Chatterjee, T.-L. Choi, D. P. Sanders, R. H. Grubbs, J. Am. Chem. Soc. 2003, 125, 11 360-11 370;
199. b) H. E. Blackwell, D. J. O'Leary, A. K. Chatterjee, R. A. Washenfelder, D. A. Bussmann, R. H. Grubbs, J. Am. Chem. Soc. 2000, 122, 58-71.
200. For reviews of the glycopeptide antibiotics, see: a) K. C. Nicolaou, C. N. C. Boddy, S. Bräse, N. Winssinger, Angew. Chem. 1999, 111, 2230-2287;
201. Angew. Chem. Int. Ed. 1999, 38, 2096-2152;
202. b) D. H. Williams, B. Bardsley, Angew. Chem. 1999, 111, 1264-1286;
203. Angew. Chem. Int. Ed. 1999, 38, 1172-1193.
204. a) K. C. Nicolaou, S. Y. Cho, R. Hughes, N. Winssinger, C. Smethurst, H. Labischinski, R. Endermann, Chem. Eur. J. 2001, 7, 3798-3823;
205. b) K. C. Nicolaou, R. Hughes, S. Y. Cho, N. Winssinger, H. Labischinski, R. Endermann, Chem. Eur. J. 2001, 7, 3824-3843.
206. The Schreiber group pioneered this strategy of dimerization of biologically relevant compounds through alkene cross-metathesis in their synthesis of novel dimers of the immunosuppressant FK506: S. T. Diver, S. L. Schreiber, J. Am. Chem. Soc. 1997, 119, 5106-5109.
207. For representative references, see: a) D. Bradley, Drug Discovery Today 2000, 5, 44-45;
208. b) S. J. Sucheck, A. L. Wong, K. M. Koeller, D. D. Boehr, K. Draker, P. Sears, G. D. Wright, C.-H. Wong, J. Am. Chem. Soc. 2000, 122, 5230-5231;
209. c) P. J. Loll, A. E. Bevivino, B. D. Korty, P. H. Axelsen, J. Am. Chem. Soc. 1997, 119, 1516-1522;
210. d) J. P. Mackay, U. Gerhard, D. A. Beauregard, R. A. Maplestone, D. H. Williams, J. Am. Chem. Soc. 1994, 116, 4573-4580.
211. a) D. H. Williams, A. J. Maguire, W. Tsuzuki, M. S. Westwell, Science 1998, 280, 711-714;
212. b) J. P. Mackay, U. Gerhard, D. A. Beauregard, M. S. Westwell, M. S. Searle, D. H. Williams, J. Am. Chem. Soc. 1994, 116, 4581-4590;
213. c) U. Gerhard, J. P. Mackay, R. A. Maplestone, D. H. Williams, J. Am. Chem. Soc. 1993, 115, 232-237.
214. For an entry to this field, see the following papers and references therein: a) J.-M. Lehn, A. V. Eliseev, Science 2001, 291, 2331-2332;
215. b) G. R. L. Cousins, R. L. E. Furlan, Y.-F. Ng, J. E. Redman, J. K. M. Sanders, Angew. Chem. 2001, 113, 437-442;
216. Angew. Chem. Int. Ed. 2001, 40, 423-428;
217. c) H. Hioki, W. C. Still, J. Org. Chem. 1998, 63, 904-905;
218. d) T. Giger, M. Wigger, S. Audétat, S. A. Benner, Synlett 1998, 688-691.
219. a) Z. Xiong, E. J. Corey, J. Am. Chem. Soc. 2000, 122, 4831-4832;
220. b) Z. Xiong, E. J. Corey, J. Am. Chem. Soc. 2000, 122, 9328-9329.
221. For selected recent reviews of approaches in biomimetic synthesis, see: a) M. C. de la Torre, M. A. Sierra, Angew. Chem. 2003, 115, 162-184;
222. Angew. Chem. Int. Ed. 2003, 42, 160-181;
223. b) K. C. Nicolaou, T. Montagnon, S. A. Snyder, Chem. Commun. 2003, 551-564;
224. c) U. Scholz, E. Winterfeldt, Nat. Prod. Rep. 2000, 17, 349-366.
225. For selected recent examples of biomimetic syntheses, see: a) B. Gerard, G. Jones II, J. A. Porco, Jr., J. Am. Chem. Soc. 2004, 126, 13 620-13 621;
226. b) S. K. Bagal, R. M. Adlington, J. E. Baldwin, R. Marquez, J. Org. Chem. 2004, 69, 9100-9108;
227. c) G. Vassilikogiannakis, M. Stratakis, Angew. Chem. 2003, 115, 5623-5626;
228. Angew. Chem. Int. Ed. 2003, 42, 5465-5468;
229. d) B. M. Trost, H. C. Shen, J.-P. Surivet, Angew. Chem. 2003, 115, 4073-4077;
230. Angew. Chem. Int. Ed. 2003, 42, 3943-3947.
231. The synthesis of compound 77 was reported by the Kodama group, who confirmed that it did not correspond to the natural product, soon after the initial disclosure by the Corey group: H. Hioki, C. Kanehara, Y. Ohnishi, Y. Umemori, H. Sakai, S. Yoshio, M. Matsushita, M. Kodama, Angew. Chem. 2000, 112, 2652-2654;
232. Angew. Chem. Int. Ed. 2000, 39, 2552-2554.
233. The total synthesis and structure revision of glabrescol was first reported by the Morimoto group, who had to prepare a similarly large number of incorrect stereoisomers, a few weeks prior to the corresponding disclosure by the Corey group: Y. Morimoto, T. Iwai, T. Kinoshita, J. Am. Chem. Soc. 2000, 122, 7124-7125.
234. Molecular-modeling studies subsequently indicated that the originally proposed structure does not correspond to the most thermodynamically favorable form: B. R. Bellenie, J. M. Goodman, Tetrahedron Lett. 2001, 42, 7477-7479.
235. The Smith group has reported an elegant total synthesis of (-)-cylindrocyclophanes A and F by employing a novel tandem alkene cross-metathesis dimerization/ring-closing-metathesis strategy: A. B. Smith, C. M. Adams, S. A. Kozmin, D. V. Paone, J. Am. Chem. Soc. 2001, 123, 5925-5937;
236. for a discussion of this and other cross-metathesis strategies, see reference [7b], pp. 178-184.
237. The structure originally proposed for amphidinolide W (86) was the 6S diastereoisomer, which was also synthesized by the Ghosh group and shown to be different from the natural product.
238. a) K. C. Nicolaou, S. Vyskocil, T. V. Koftis, Y. M. A. Yamada, T. Ling, D. Y.-K. Chen, W. Tang, G. Petrovic, M. O. Frederick, Y. Li, M. Satake, Angew. Chem. 2004, 116, 4412-4418;
239. Angew. Chem. Int. Ed. 2004, 43, 4312-4318;
240. b) K. C. Nicolaou, T. V. Koftis, S. Vyskocil, G. Petrovic, T. Ling, Y. M. A. Yamada, W. Tang, M. O. Frederick, Angew. Chem. 2004, 116, 4418-4424;
241. Angew. Chem. Int. Ed. 2004, 43, 4318-4324.
242. 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;
243. Angew. Chem. Int. Ed. 2003, 42, 3643-3648;
244. 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;
245. Angew. Chem. Int. Ed. 2003, 42, 3649-3653.
246. A somewhat similar cross-metathesis strategy proceeded much less efficiently in model studies towards the synthesis of ciguatoxin CTX: H. Oguri, S. Sasaki, T. Oishi, M. Hirama, Tetrahedron Lett. 1999, 40, 5405-5408.
247. a) J. E. Baldwin, presented at The Scripps Research Institute, La Jolla, 6th December 2004;
248. b) M. F. Jacobsen, J. E. Moses, R. M. Adlington, J. E. Baldwin, Org. Lett. 2005, 7, 2473-2476.
249. See C. M. Beaudry, D. Trauner, Org. Lett. 2002, 4, 2221-2224, and references therein.
250. K. A. Parker, Y.-H. Lim, J. Am. Chem. Soc. 2004, 126, 15 968-15 969.
251. J. E. Banfield, D. St. C. Black, S. R. Johns, R. I. Willing, Aust. J. Chem. 1982, 35, 2247-2256, and references therein.
252. a) K. C. Nicolaou, N. A. Petasis, R. E. Zipkin, J. Uenishi, J. Am. Chem. Soc. 1982, 104, 5555-5557;
253. b) K. C. Nicolaou, N. A. Petasis, J. Uenishi, R. E. Zipkin, J. Am. Chem. Soc. 1982, 104, 5557-5558;
254. c) K. C. Nicolaou, R. E. Zipkin, N. A. Petasis, J. Am. Chem. Soc. 1982, 104, 5558-5560;
255. d) K. C. Nicolaou, N. A. Petasis, R. E. Zipkin, J. Am. Chem. Soc. 1982, 104, 5560-5562.
256. K. Kakinuma, C. A. Hanson, K. L. Rinehart, Jr., Tetrahedron 1976, 32, 212-222.
257. J. E. Moses, J. E. Baldwin, R. Marquez, R. M. Adlington, A. R. Cowley, Org. Lett. 2002, 4, 3731-3734.
258. C. Morrill, R. H. Grubbs, J. Org. Chem. 2003, 68, 6031-6034.
259. Danishefsky and co-workers applied similar methodology in the synthesis of Suzuki macrocyclization precursors of novel epothilone analogues: J. T. Njardarson, K. Biswas, S. J. Danishefsky, Chem. Commun. 2002, 23, 2759-2761.
260. For the first application of a selective mono-cross-coupling reaction of a 1,1-dibromoalkene, see: W. R. Roush, R. Riva, J. Org. Chem. 1988, 53, 710-713.
261. C. Dai, G. C. Fu, J. Am. Chem. Soc. 2001, 123, 2719-2724.
262. For a discussion of the reasoning behind the particular choice of a palladium(II) species to effect this isomerization, see reference [117].
263. J. Limanto, M. L. Snapper, J. Am. Chem. Soc. 2000, 122, 8071-8072.
264. P. A. Wender, N. C. Ihle, C. R. D. Correia, J. Am. Chem. Soc. 1988, 110, 5904-5906.
265. Two other total syntheses of asteriscanolide, both employing ring-closing-metathesis reactions to construct the eight-membered ring, have been reported: a) M. E. Krafft, Y. Y. Cheung, K. A. Abboud, J. Org. Chem. 2001, 66, 7443-7448;
266. b) M. E. Krafft, Y. Y. Cheung, C. A. Juliano-Capucao, Synthesis 2000, 1020-1026;
267. c) L. A. Paquette, J. Tae, M. P. Arrington, A. H. Sadoun, J. Am. Chem. Soc. 2000, 122, 2742-2748.
268. R. Grigg, M. York, Tetrahedron Lett. 2000, 41, 7255-7258, and references therein.
269. J. R. Stille, R. H. Grubbs, J. Am. Chem. Soc. 1986, 108, 855-856.
270. a) F. N. Tebbe, G. W. Parshall, G. S. Reddy, J. Am. Chem. Soc. 1978, 100, 3611-3613;
271. b) F. N. Tebbe, G. W. Parshall, D. W. Ovenall, J. Am. Chem. Soc. 1979, 101, 5074-5075.
272. K. A. Brown-Wensley, S. L. Buchwald, L. Cannizzo, L. Clawson, S. Ho, D. Meinhardt, J. R. Stille, D. Straus, R. H. Grubbs, Pure Appl. Chem. 1983, 55, 1733-1744.
273. D. A. Straus, R. H. Grubbs, J. Mol. Catal. 1985, 28, 9-19.
274. F. N. Tebbe, G. W. Parshall, D. W. Ovenall, J. Am. Chem. Soc. 1979, 101, 5074-5075.
275. More recently, dimethyltitanocene has been introduced as a more easily handled equivalent of the Tebbe reagent: N. A. Petasis, S.-P. Lu, E. I. Bzowej, D.-K. Fu, J. P. Staszewski, I. Adritopoulou-Zanze, M. A. Petane, Y.-H. Hu, Pure Appl. Chem. 1996, 68, 667-670.
276. The Lebel group has recently reported novel one-pot methylenation/ring- closing-metathesis protocols that employ sequential rhodium- and ruthenium-based catalysts: H. Lebel, V. Paquet, J. Am. Chem. Soc. 2004, 126, 11 152-11 153.
277. K. C. Nicolaou, M. H. D. Postema, C. F. Claiborne, J. Am. Chem. Soc. 1996, 118, 1565-1566.
278. K. C. Nicolaou, M. H. D. Postema, E. W. Yue, A. Nadin, J. Am. Chem. Soc. 1996, 118, 10335-10336.
279. H. W. B. Johnson, U. Majumder, J. D. Rainier, J. Am. Chem. Soc. 2005, 127, 848-849.
280. a) J. M. Cox, J. D. Rainier, Org. Lett. 2001, 3, 2919-2922;
281. b) U. Majumder, J. M. Cox, J. D. Rainier, Org. Lett. 2003, 5, 913-916.
282. K. Takai, T. Kakiuchi, Y. Kataoka, K. Utimoto, J. Org. Chem. 1994, 59, 2668-2670.
283. For other total syntheses of gambierol, see: a) I. Kadota, H. Takamura, K. Sato, A. Ohno, K. Matsuda, Y. Yamamoto, J. Am. Chem. Soc. 2003, 125, 46-47;
284. b) I. Kadota, H. Takamura, K. Sato, A. Ohno, K. Matsuda, M. Satake, Y. Yamamoto, J. Am. Chem. Soc. 2003, 125, 11 893-11 899;
285. c) H. Fuwa, N. Kainuma, K. Tachibana, M. Sasaki, J. Am. Chem. Soc. 2002, 124, 14 983-14 992, and references therein.
286. K. C. Nicolaou, J. A. Vega, G. Vassilikogiannakis, Angew. Chem. 2001, 113, 4573-4577;
287. Angew. Chem. Int. Ed. 2001, 40, 4441-4445.
288. W. J. Zuercher, M. Hashimoto, R. H. Grubbs, J. Am. Chem. Soc. 1996, 118, 6634-6640.
289. R. Stragies, S. Blechert, J. Am. Chem. Soc. 2000, 122, 9584-9591.
290. M. Schaudt, S. Blechert, J. Org. Chem. 2003, 68, 2913-2920.
291. C. Stapper, S. Blechert, J. Org. Chem. 2002, 67, 6456-6460.
292. A. V. Statsuk, D. Liu, S. A. Kozmin, J. Am. Chem. Soc. 2004, 126, 9546-9547.
293. For examples, see: a) D. J. Wallace, Tetrahedron Lett. 2003, 44, 2145-2148;
294. b) M.-P. Heck, C. Baylon, S. P. Nolan, C. Mioskowski, Org. Lett. 2001, 3, 1989-1991;
295. c) S. Ma, B. Ni, Org. Lett. 2002, 4, 639-641;
296. d) D. J. Wallace, C. J. Cowden, D. J. Kennedy, M. S. Ashwood, I. F. Cottrell, U.-H. Dolling, Tetrahedron Lett. 2000, 41, 2027-2029;
297. e) B. Schmidt, H. Wilsemann, J. Org. Chem. 2000, 65, 5817-5822;
298. f) D. J. Wallace, P. G. Bulger, D. J. Kennedy, M. S. Ashwood, I. F. Cottrell, U.-H. Dolling, Synlett 2001, 357-360.
299. J. L. Piper, M. H. D. Postema, J. Org. Chem. 2004, 69, 7395-7398.
300. For example, see: J. Louie, R. H. Grubbs, Organometallics 2002, 21, 2153-2164.
301. For the successful employment of enol ether ring-closing metathesis in the total syntheses of trilobolide, nortrilobolide, and thapsivillosin F, see: S. F. Oliver, K. Högenauer, O. Simic, A. Antonello, M. D. Smith, S. V. Ley, Angew. Chem. 2003, 115, 6178-6182;
302. Angew. Chem. Int. Ed. 2003, 42, 5996-6000.
303. a) B. Alcaide, P. Almendros, Chem. Eur. J. 2003, 9, 1258-1262, and references therein;
304. b) B. Schmidt, Eur. J. Org. Chem. 2004, 1865-1880, and references therein.
305. It should be recalled that a number of useful non-metathesis-based carbon-carbon bond-forming reactions are catalyzed by other ruthenium complexes; for reviews, see: a) S. Dérien, F. Monnier, P. H. Dixneuf, Top. Organomet. Chem. 2004, 7, 1-44;
306. b) B. Schmidt, Angew. Chem. 2003, 115, 5146-5149;
307. Angew. Chem. Int. Ed. 2003, 42, 4996-4999;
308. c) B. M. Trost, F. D. Toste, A. B. Pinkerton, Chem. Rev. 2001, 101, 2067-2096.
309. J. Louie, C. W. Bielawski, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 11 312-11 313.
310. A related, but stepwise, metathesis-based approach to the synthesis of (-)-muscone has also been reported: a) V. P. Kamat, H. Hagiwara, T. Katsumi, T. Hoshi, T. Suzuki, M. Ando, Tetrahedron 2000, 56, 4397-4403;
311. b) V. P. Kamat, H. Hagiwara, T. Suzuki, M. Ando, J. Chem. Soc. Perkin Trans. 1 1998, 2253-2254.
312. For a novel ring-closing tandem catalysis approach to the synthesis of (+)-muscopyridine, see: A. Fürstner, A. Leitner, Angew. Chem. 2003, 115, 320-323;
313. Angew. Chem. Int. Ed. 2003, 42, 308-311.
314. D. J. Wallace, J. M. Goodman, D. J. Kennedy, A. J. Davies, C. J. Cowden, M. S. Ashwood, I. F. Cottrell, U.-H. Dolling, P. J. Reider, Org. Lett. 2001, 3, 671-674.
315. For the first examples of diastereoselective ring-closing-metathesis reactions, see: C. M. Huwe, J. Velder, S. Blechert, Angew. Chem. 1996, 108, 2542-2544;
316. Angew. Chem. Int. Ed. Engl. 1996, 35, 2376-2378.
317. J. J. Kulagowski, N. R. Curtis, C. J. Swain, B. J. Williams, Org. Lett. 2001, 3, 667-670.
318. T. J. Seiders, D. W. Ward, R. H. Grubbs, Org. Lett. 2001, 3, 3225-3228.
319. a) A. H. Hoveyda, R. R. Schrock in Organic Synthesis Highlights V (Eds.: H.-G. Schmalz, T. Wirth), Wiley-VCH, Weinheim, 2003, pp. 210-229;
320. b) A. H. Hoveyda, R. R. Schrock, Chem. Eur. J. 2001, 7, 945-950;
321. see also A. H. Hoveyda, Top. Organomet. Chem. 1998, 1, 105-132.
322. a) G. S. Weatherhead, G. A. Cortez, R. R. Schrock, A. H. Hoveyda, Proc. Natl. Acad. Sci. USA 2004, 101, 5805-5809;
323. the first such application in total synthesis was in that of (+)-endo-brevicomin: b) S. D. Burke, N. Müller, C. M. Beaudry, Org. Lett. 1999, 1, 1827-1829.
324. The Schrock-type molybdenum carbene based catalyst systems, although extremely active in alkene-metathesis reactions, have not found gainful use in the corresponding enyne-metathesis processes; for illustrative examples, see: a) M. P. Schramm, D. S. Reddy, S. A. Kozmin, Angew. Chem. 2001, 113, 4404-4407;
325. Angew. Chem. Int. Ed. 2001, 40, 4274-4277;
326. b) S.-H. Kim, W. J. Zuercher, N. B. Bowden, R. H. Grubbs, J. Org. Chem. 1996, 61, 1073-1081.
327. A. Kinoshita, M. Mori, Synlett 1994, 1020-1022.
328. a) A. Kinoshita, M. Mori, J. Org. Chem. 1996, 61, 8356-8357;
329. b) A. Kinoshita, M. Mori, Heterocycles 1997, 46, 287-299.
330. For other total syntheses of stemoamide, see: a) M. P. Sibi, T. Subramanian, Synlett 2004, 1211-1214;
331. b) M. K. Gurjar, D. S. Reddy, Tetrahedron Lett. 2002, 43, 295-298;
332. c) P. A. Jacobi, K. Lee, J. Am. Chem. Soc. 2000, 122, 4295-4303;
333. d) D. R. Williams, J. P. Reddy, G. S. Amato, Tetrahedron Lett. 1994, 35, 6417-6420.
334. a) J. B. Brenneman, R. Machauer, S. F. Martin, Tetrahedron 2004, 60, 7301-7314;
335. b) J. B. Brenneman, S. F. Martin, Org. Lett. 2004, 6, 1329-1331.
336. M. Mori, T. Tomita, Y. Kita, T. Kitamura, Tetrahedron Lett. 2004, 45, 4397-4399.
337. P. Thomas, M. Stephens, G. Wilkie, M. Amar, G. G. Lunt, P. Whiting, T. Gallagher, E. Pereira, M. Alkondon, E. X. Alburquerque, S. J. Wannacott, J. Neurochem. 1993, 60, 2308-2311.
338. For a review of synthetic approaches to and total syntheses of anatoxin-a up to mid-1996, see: H. L. Mansell, Tetrahedron 1996, 52, 6025-6061.
339. For total syntheses of anatoxin-a since mid-1996, see: a) T. Wegge, S. Schwarz, G. Seitz, Tetrahedron: Asymmetry 2000, 11, 1405-1410;
340. b) P. J. Parsons, N. P. Camp, N. Edwards, L. R. Sumoreeah, Tetrahedron 1999, 55, 309-315;
341. c) V. K. Aggarwal, P. S. Humphries, A. Fenwick, Angew. Chem. 1999, 111, 2178-2180;
342. Angew. Chem. Int. Ed. 1999, 38, 1985-1986;
343. d) B. M. Trost, J. D. Oslob, J. Am. Chem. Soc. 1999, 121, 3057-3064;
344. e) C.-Y. Oh, K.-S. Kim, W.-H. Ham, Tetrahedron Lett. 1998, 39, 2133-2136;
345. f) P. J. Parsons, N. P. Camp, M. J. Underwood, D. M. Harvey, Tetrahedron 1996, 52, 11 637-11 642.
346. For selected examples of the formation of bridged aza-bicyclic structures by ring-closing metathesis, see the relevant citations in reference [165b].
347. For a review of allylic 1,3-strain as a controlling factor in stereoselective transformations, see: R. W. Hoffmann, Chem. Rev. 1989, 89, 1841-1860.
348. V. K. Aggarwal, C. J. Astle, M. Roger-Evans, Org. Lett. 2004, 6, 1469-1471.
349. a) E. C. Hansen, D. Lee, J. Am. Chem. Soc. 2004, 126, 15 074-15 080;
350. b) E. C. Hansen, D. Lee, J. Am. Chem. Soc. 2003, 125, 9582-9583.
351. M. Mori, N. Sakakibara, A. Kinoshita, J. Org. Chem. 1998, 63, 6082-6083.
352. For examples of enyne-metathesis macrocyclizations under an atmosphere of ethylene, see: A. G. M. Barrett, A. J. Hennessy, R. L. Vezouet, P. A. Procopiou, P. W. Searle, S. Stefaniak, R. J. Upton, A. J. P. White, D. J. Williams, J. Org. Chem. 2004, 69, 1028-1037.
353. Alternative reasons, including maintaining the reactivity of the catalyst, have been invoked for the beneficial effect of ethylene on ring-closing enyne-metathesis reactions to generate common- and medium-sized ring systems, since these reactions invariably still yield the corresponding 1,2-disubstituted cyclic products and are not believed to involve the two-step process; for a discussion, see reference [174].
354. a) C. A. Morales, M. E. Layton, M. D. Shair, Proc. Natl. Acad. Sci. USA 2004, 101, 12 036-12 041;
355. b) M. E. Layton, C. A. Morales, M. D. Shair, J. Am. Chem. Soc. 2002, 124, 773-775.
356. a) X. Fu, M. B. Hossain, F. J. Schmitz, D. van der Helm, J. Org. Chem. 1997, 62, 3810-3819;
357. b) X. Fu, M. B. Hossain, D. van der Helm, F. J. Schmitz, J. Am. Chem. Soc. 1994, 116, 12 125-12 126.
358. For conceptually related uses of temporary directing groups to effect atropselective macrocyclizations in the synthesis of vancomycin, see: a) D. A. Evans, C. J. Dinsmore, P. S. Watson, M. R. Wood, T. I. Richardson, B. W. Trotter, J. L. Katz, Angew. Chem. 1998, 110, 2868-2872;
359. Angew. Chem. Int. Ed. 1998, 37, 2704-2708;
360. b) K. C. Nicolaou, C. N. C. Boddy, J. Am. Chem. Soc. 2002, 124, 10451-10455.
361. A similar observation had been reported previously in a ring-closing alkene-metathesis reaction: D. Joe, L. E. Overman, Tetrahedron Lett. 1997, 38, 8635-8638.
362. B. M. Trost, G. A. Doherty, J. Am. Chem. Soc. 2000, 122, 3801-3810.
363. For a Review of the chemistry and biology of roseophilin and the prodigiosin alkaloids, in which five different ring-closing-metathesis approaches to roseophilin are highlighted, see: A. Fürstner, Angew. Chem. 2003, 115, 3706-3728;
364. Angew. Chem. Int. Ed. 2003, 42, 3582-3603.
365. a) A. Fürstner, H. Weintritt, J. Am. Chem. Soc. 1998, 120, 2817-2825;
366. b) A. Fürstner, T. Gastner, H. Weintritt, J. Org. Chem. 1999, 64, 2361-2366.
367. For a discussion of the plausible mechanistic pathways of these types of enyne-metathesis reactions, see: A. Fürstner, H. Szillat, B. Gabor, M. Mynott, J. Am. Chem. Soc. 1998, 120, 8305-8314, and references therein.
368. For a discussion of the reorganization of enyne systems catalyzed by platinum salts, see: L. Añorbe, G. Domínguez, J. Pérez-Castells, Chem. Eur. J. 2004, 10, 4938-4943.
369. a) S.-H. Kim, N. Bowden, R. H. Grubbs, J. Am. Chem. Soc. 1994, 116, 10 801-10 802;
370. b) S.-H. Kim, W. J. Zuercher, N. B. Bowden, R. H. Grubbs, J. Org. Chem. 1996, 61, 1073-1081.
371. W. J. Zuercher, M. Scholl, R. H. Grubbs, J. Org. Chem. 1998, 63, 4291-4298.
372. F.-D. Boyer, I. Hanna, L. Ricard, Org. Lett. 2004, 6, 1817-1820.
373. a) D. S. Tan, G. B. Dudley, S. J. Danishefsky, Angew. Chem. 2002, 114, 2289-2292;
374. Angew. Chem. Int. Ed. 2002, 41, 2185-2188;
375. b) S. Lin, G. B. Dudley, D. S. Tan, S. J. Danishefsky, Angew. Chem. 2002, 114, 2292-2295;
376. Angew. Chem. Int. Ed. 2002, 41, 2188-2191.
377. B. Shi, N. A. Hawryluk, B. B. Snider, J. Org. Chem. 2003, 68, 1030-1042.
378. F.-D. Boyer, I. Hanna, Tetrahedron Lett. 2002, 43, 7569-7572.
379. For the application of an enyne-metathesis cascade process in the synthesis of erythrocarine, see: K. Shimizu, M. Takimoto, M. Mori, Org. Lett. 2003, 5, 2323-2325.
380. S. T. Diver, A. J. Giessert, Synthesis 2004, 466-471.
381. a) M. Mori, K. Tonogaki, N. Nishiguchi, J. Org. Chem. 2002, 67, 224-226;
382. b) A. Kinoshita, N. Sakakibara, M. Mori, J. Am. Chem. Soc. 1997, 119, 12 388-12 389.
383. K. Tonogaki, M. Mori, Tetrahedron Lett. 2002, 43, 2235-2238.
384. J. A. Smulik, S. T. Diver, J. Org. Chem. 2000, 65, 1788-1792.
385. R. Stragies, M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2629-2630;
386. Angew. Chem. Int. Ed. Engl. 1997, 36, 2518-2520.
387. For examples of enyne cross-metathesis of substituted alkenes, see: H.-Y. Lee, B. G. Kim, M. L. Snapper, Org. Lett. 2003, 5, 1855-1858, and references therein.
388. For examples of enyne cross-metathesis in cascade processes, see: a) B. P. Peppers, S. T. Diver, J. Am. Chem. Soc. 2004, 126, 9524-9525;
389. b) J. A. Smulik, S. T. Diver, Tetrahedron Lett. 2001, 42, 171-174;
390. c) S. C. Schürer, S. Blechert, Chem. Commun. 1999, 1203-1204.
391. For studies towards the synthesis of the marine sponge metabolite mycothiazole A in which an enyne cross-metathesis reaction was employed to fashion a key 1,3-diene intermediate, see: S. Rodriguez-Conesa, P. Candal, C. Jiménez, J. Rodriguez, Tetrahedron Lett. 2001, 42, 6699-6702.
392. a) L. Kloppenburg, D. Song, U. H. F. Bunz, J. Am. Chem. Soc. 1998, 120, 7973-7974;
393. see also: b) K. Grela, J. Ignatowska, Org. Lett. 2002, 4, 3747-3749.
394. a) R. R. Schrock, D. N. Clark, J. Sancho, J. H. Wengrovius, S. M. Rocklage, S. F. Pedersen, Organometallics 1982, 1, 1645-1651;
395. the Schrock group were the first to report alkyne metathesis in the presence of a well-defined alkylidyne catalyst: b) J. H. Wengrovius, J. Sancho, R. R. Schrock, J. Am. Chem. Soc. 1981, 103, 3932-3934.
396. a) A. Fürstner, C. Mathes, C. W. Lehmann, J. Am. Chem. Soc. 1999, 121, 9453-9454;
397. b) A. Fürstner, C. Mathes, C. W. Lehmann, Chem. Eur. J. 2001, 7, 5299-5317.
398. A related and potentially useful molybdenum-based catalyst for alkyne metathesis was introduced by the Cummins group at about the same time, although this has not yet found widespread use in organic synthesis: Y.-C. Tsai, P. L. Diaconescu, C. C. Cummins, Organometallics 2000, 19, 5260-5262.
399. A recent modification of molybdenum catalyst precursor 237 for alkyne metathesis was recently described: W. Zhang, J. S. Moore, J. Am. Chem. Soc. 2004, 126, 12 796.
400. For examples of early applications of alkyne metathesis in organic synthesis, see: a) N. Kaneta, T. Hirai, M. Mori, Chem. Lett. 1995, 627-628;
401. b) N. Kaneta, K. Hikichi, S. Asaka, M. Uemura, M. Mori, Chem. Lett. 1995, 1055-1056.
402. A. Fürstner, G. Seidel, Angew. Chem. 1998, 110, 1758-1760;
403. Angew. Chem. Int. Ed. 1998, 57, 1734-1736.
404. A. Fürstner, O. Guth, A. Rumbo, G. Seidel, J. Am. Chem. Soc. 1999, 121, 11 108-11 113.
405. [203b]
406. For reviews of epothilone syntheses, see: a) reference [67];
407. b) C. R. Harris, S. J. Danishefsky, J. Org. Chem. 1999, 64, 8434-8456;
408. c) K. C. Nicolaou, F. Roschangar, D. Vourloumis, Angew. Chem. 1998, 110, 2120-2153;
409. Angew. Chem. Int. Ed. 1998, 37, 2014-2045.
410. A. Fürstner, C. Mathes, K. Grela, Chem. Commun. 2001, 1057-1059.
411. For further examples of the application of the alkyne ring-closing-metathesis/Lindlar reduction protocol in total synthesis, see: a) A. Fürstner, D. De Souza, L. Parra-Rapado, J. T. Jensen, Angew. Chem. 2003, 115, 5516-5518;
412. Angew. Chem. Int. Ed. 2003, 42, 5358-5360;
413. b) A. Fürstner, F. Stelzer, A. Rumbo, H. Krause, Chem. Eur. J. 2002, 8, 1856-1871;
414. c) A. Fürstner, K. Radkowski, J. Grabowski, C. Wirtz, R. Mynott, J. Org. Chem. 2000, 65, 8758-8762.
415. a) B. M. Trost, Z. T. Ball, T. Jöge, J. Am. Chem. Soc. 2002, 124, 7922-7923;
416. b) F. Lacombe, K. Radkowski, G. Seidel, A. Fürstner, Tetrahedron 2004, 60, 7315-7324;
417. c) A. Fürstner, K. Radkowski, Chem. Commun. 2002, 2182-2183.
418. For a Minireview of recent methods for the synthesis of E-alkene units in macrocyclic compounds, see reference [72].
419. A. Fürstner, A.-S. Castanet, K. Radkowski, C. W. Lehmann, J. Org. Chem. 2003, 68, 1521-1528.
420. For a review of regioselective syntheses of substituted furans, see: X. L. Hou, H. Y. Cheung, T. Y. Hon, P. L. Kwan, T. H. Lo, S. Y. Tong, H. N. C. Wong, Tetrahedron 1998, 54, 1955-2020.
421. For a previous total synthesis of citreofuran, see: S. Lai, X. Gao, Y. Shizuri, S. Yamamura, Chin. Chem. Lett. 1994, 5, 481-484.
422. For a discussion of this phenomenon as applied to related systems, see: J. A. Marshall, E. V. Van Devender, J. Org. Chem. 2001, 66, 8037-8041.
423. a) U. H. F. Bunz in Modern Arene Chemistry (Ed.: D. Astruc), Wiley-VCH, Weinheim, 2002, pp. 217-249;
424. see also: b) W. Zhang, J. S. Moore, Macromolecules 2004, 37, 3973-3975, and references therein.
425. A. Fürstner, T. Dierkes, Org. Lett. 2000, 2, 2463-2464.
426. A. Fürstner, K. Langemann, J. Am. Chem. Soc. 1997, 119, 9130-9136.
427. A. Fürstner, K. Grela, C. Mathes, C. W. Lehmann, J. Am. Chem. Soc. 2000, 122, 11 799-11 805.
428. R. Noyori, M. Suzuki, Angew. Chem. 1984, 96, 854-883;
429. Angew. Chem. Int. Ed. Engl. 1984, 23, 847-876.
430. For an application of alkyne cross-metathesis in studies towards the total syntheses of (-)-terpestacin and siccanol by the Jamison group, see: J. Chan, T. F. Jamison, J. Am. Chem. Soc. 2004, 126, 10 682-10 691.