Click Chemistry: Diverse Chemical Function from a Few Good Reactions

Angewandte Chemie - International Edition

Volumn 40, Issue 11, 2001, Pages 2004-2021

  Kolb, Hartmuth C ^b   Finn, M G ^a   Sharpless, K Barry ^a  

^a SCRIPPS RESEARCH INSTITUTE   (United States)

^b Coclacanth Corporation ^*  (United States)

Author keywords

Combinatorial chemistry; Drug research; Synthesis design; Water chemistry

Indexed keywords

EID: 0000096835     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3773(20010601)40:11<2004::AID-ANIE2004>3.0.CO;2-5     Document Type: Review

References (233)

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4. For reviews, see: a) I. T. Baldwin, C. A. Preston, Planta 1999, 208, 137-145; b) O. C. Yoder, Dev. Plant Pathol. 1998, 13, 3-15: c) T. Hartmann, Entomol. Exp. Appl. 1996, 80, 177-188; d) E. Haslam, Chemoecology 1995, 5/6, 89-95; for a review of antifeedant secondary metabolites, see: D. P. Singh, A. K. Pant, R. K. Rai, Chem. Environ. Res. 1993, 2, 3-18.
5. For reviews, see: a) I. T. Baldwin, C. A. Preston, Planta 1999, 208, 137-145; b) O. C. Yoder, Dev. Plant Pathol. 1998, 13, 3-15: c) T. Hartmann, Entomol. Exp. Appl. 1996, 80, 177-188; d) E. Haslam, Chemoecology 1995, 5/6, 89-95; for a review of antifeedant secondary metabolites, see: D. P. Singh, A. K. Pant, R. K. Rai, Chem. Environ. Res. 1993, 2, 3-18.
6. For reviews, see: a) I. T. Baldwin, C. A. Preston, Planta 1999, 208, 137-145; b) O. C. Yoder, Dev. Plant Pathol. 1998, 13, 3-15: c) T. Hartmann, Entomol. Exp. Appl. 1996, 80, 177-188; d) E. Haslam, Chemoecology 1995, 5/6, 89-95; for a review of antifeedant secondary metabolites, see: D. P. Singh, A. K. Pant, R. K. Rai, Chem. Environ. Res. 1993, 2, 3-18.
7. For reviews, see: a) I. T. Baldwin, C. A. Preston, Planta 1999, 208, 137-145; b) O. C. Yoder, Dev. Plant Pathol. 1998, 13, 3-15: c) T. Hartmann, Entomol. Exp. Appl. 1996, 80, 177-188; d) E. Haslam, Chemoecology 1995, 5/6, 89-95; for a review of antifeedant secondary metabolites, see: D. P. Singh, A. K. Pant, R. K. Rai, Chem. Environ. Res. 1993, 2, 3-18.
8. For reviews, see: a) I. T. Baldwin, C. A. Preston, Planta 1999, 208, 137-145; b) O. C. Yoder, Dev. Plant Pathol. 1998, 13, 3-15: c) T. Hartmann, Entomol. Exp. Appl. 1996, 80, 177-188; d) E. Haslam, Chemoecology 1995, 5/6, 89-95; for a review of antifeedant secondary metabolites, see: D. P. Singh, A. K. Pant, R. K. Rai, Chem. Environ. Res. 1993, 2, 3-18.
9. For an eloquent account of the history of medicinal chemistry, see: W. Sneader, Drug Prototypes and their Exploitation, Wiley, New York, 1996. Here Sneader traces the origins of modern medicines back to approximately 200 natural product prototypes, the majority of which are toxic secondary metabolites created by plants and microorganisms for self-defense.
10. Some delightful exceptions do exist, such as Celebrex (celecoxib): T. D. Penning, J. J. Talley, S. R. Bertenshaw, J. S. Carter, P. W. Collins, S. Docter, M. J. Graneto, L. F. Lee, J. W. Malecha, J. M. Miyashiro, R. S. Rogers, D. J. Rogier, S. S. Yu, G. D. Anderson, E. G. Burton, J. N. Cogburn, S. A. Gregory, C. M. Koboldt, W. E. Perkins, K. Seibert, A. W. Veenhuizen, Y. Y. Zhang, P. C. Isakson, J. Med. Chem. 1997, 40, 1347-1365.
11. Structure elucidation: G. Albers-Schönberg, B. H. Arison, O. D. Hensens, J. Hirshfield, K. Hoogsteen, E. A. Kaczka, R. E. Rhodes, J. S. Kahan, F. M. Kahan, R. W. Ratcliffe, E. Walton, L. J. Ruswinkle, R. B. Morin, B. G. Christensen, J. Am. Chem. Soc. 1978, 100, 6491-6499.
12. Antibacterial properties: F. P. Tally, N. V. Jacobus, S. L. Gorbach, Antimicrob. Agents Chemother. 1978, 14, 436-438; S. S. Weaver, G. P. Bodey, B. M. LeBlanc, Antimicrob. Agents Chemother. 1979, 15, 518- 521; J.S. Kahan, F.M. Kahan, R. Goegelman, S.A. Currie, M. Jackson, E.O. Stapley, T.W. Miller, A.K. Miller, D. Hendlin, S. Mochales, S. Hernandez, H.B. Woodruff, J. Birnbaum, J. Antibiot. 1979, 32, 1-12.
13. Antibacterial properties: F. P. Tally, N. V. Jacobus, S. L. Gorbach, Antimicrob. Agents Chemother. 1978, 14, 436-438; S. S. Weaver, G. P. Bodey, B. M. LeBlanc, Antimicrob. Agents Chemother. 1979, 15, 518-521; J.S. Kahan, F.M. Kahan, R. Goegelman, S.A. Currie, M. Jackson, E.O. Stapley, T.W. Miller, A.K. Miller, D. Hendlin, S. Mochales, S. Hernandez, H.B. Woodruff, J. Birnbaum, J. Antibiot. 1979, 32, 1-12.
14. Antibacterial properties: F. P. Tally, N. V. Jacobus, S. L. Gorbach, Antimicrob. Agents Chemother. 1978, 14, 436-438; S. S. Weaver, G. P. Bodey, B. M. LeBlanc, Antimicrob. Agents Chemother. 1979, 15, 518- 521; J.S. Kahan, F.M. Kahan, R. Goegelman, S.A. Currie, M. Jackson, E.O. Stapley, T.W. Miller, A.K. Miller, D. Hendlin, S. Mochales, S. Hernandez, H.B. Woodruff, J. Birnbaum, J. Antibiot. 1979, 32, 1-12.
15. Process optimization: D. G. Melillo, I. Shinkai, T. Liu, K. Ryan, M. Sletzinger, Tetrahedron Lett. 1980, 21, 2783-2786; I. Shinkai, T. Liu, R. A. Reamer, M. Sletzinger, Tetrahedron Lett. 1982, 23, 4899-4902; see also: D. L. Hughes, R. A. Reamer, J. J. Bergan, E. J. J. Grabowski, J. Am. Chem. Soc. 1988, 110, 6487-6491.
16. Process optimization: D. G. Melillo, I. Shinkai, T. Liu, K. Ryan, M. Sletzinger, Tetrahedron Lett. 1980, 21, 2783-2786; I. Shinkai, T. Liu, R. A. Reamer, M. Sletzinger, Tetrahedron Lett. 1982, 23, 4899-4902; see also: D. L. Hughes, R. A. Reamer, J. J. Bergan, E. J. J. Grabowski, J. Am. Chem. Soc. 1988, 110, 6487-6491.
17. Process optimization: D. G. Melillo, I. Shinkai, T. Liu, K. Ryan, M. Sletzinger, Tetrahedron Lett. 1980, 21, 2783-2786; I. Shinkai, T. Liu, R. A. Reamer, M. Sletzinger, Tetrahedron Lett. 1982, 23, 4899-4902; see also: D. L. Hughes, R. A. Reamer, J. J. Bergan, E. J. J. Grabowski, J. Am. Chem. Soc. 1988, 110, 6487-6491.
18. a) Meropenem synthesis: M. Sunagawa, H. Matsumura, T. Inoue, M. Fukasawa, K. Masatomo, M. Kato, EU-A EP126587, 1984; A. S. Prashad, N. Vlahos, P. Fabio, G. B. Feigelson, Tetrahedron Lett. 1998, 39, 7035-7038;
19. a) Meropenem synthesis: M. Sunagawa, H. Matsumura, T. Inoue, M. Fukasawa, K. Masatomo, M. Kato, EU-A EP126587, 1984; A. S. Prashad, N. Vlahos, P. Fabio, G. B. Feigelson, Tetrahedron Lett. 1998, 39, 7035-7038;
20. b) structure-activity discussion: M. Sunagawa, H. Matsumura, T. Inoue, M. Fukasawa, M. Kato, J. Antibiot. 1990, 43, 519-532.
21. a) Synthesis: D. B. R. Johnston, S. M. Schmitt, F. A. Bouffard, B. G. Christensen, J. Am. Chem. Soc. 1978, 100, 313-315; T. N. Salzmann, R. W. Ratcliffe, B. G. Christensen, F. A. Bouffard, J. Am. Chem. Soc. 1980, 102, 6161-6163;
22. a) Synthesis: D. B. R. Johnston, S. M. Schmitt, F. A. Bouffard, B. G. Christensen, J. Am. Chem. Soc. 1978, 100, 313-315; T. N. Salzmann, R. W. Ratcliffe, B. G. Christensen, F. A. Bouffard, J. Am. Chem. Soc. 1980, 102, 6161-6163;
23. b) S. Redshaw, G. J. Thomas, Emerging Drugs 1997, 2, 127-154.
24. 4 = 2 560 000 reaction products, which is quite a high figure considering that it is of the same order of magnitude as the total number of chemical compounds described to date." (G. Gokel, G. Lüdke, I. Ugi, in Isonitrile Chemistry (Ed.: 1. Ugi), Academic Press, New York, 1971, pp. 145-199; see also: I. Ugi, R. Meyr, U. Fetzer, C. Steinbrückner, Angew. Chem. 1959, 71, 386). When the pharmaceutical industry "discovered" combinatorial chemistry about 20 years later, the solid-phase approach, pioneered by Merrifield for multistep synthesis of large biopolymers, was adapted for multistep syntheses of druglike molecules. Only recently, following ArQule's lead, has the drug-discovery community realized the power of Ugi's vision for quickly generating molecular diversity through robust, yet simple, reaction cascades that assemble multiple components in solution.
25. 4 = 2 560 000 reaction products, which is quite a high figure considering that it is of the same order of magnitude as the total number of chemical compounds described to date." (G. Gokel, G. Lüdke, I. Ugi, in Isonitrile Chemistry (Ed.: 1. Ugi), Academic Press, New York, 1971, pp. 145-199; see also: I. Ugi, R. Meyr, U. Fetzer, C. Steinbrückner, Angew. Chem. 1959, 71, 386). When the pharmaceutical industry "discovered" combinatorial chemistry about 20 years later, the solid-phase approach, pioneered by Merrifield for multistep synthesis of large biopolymers, was adapted for multistep syntheses of druglike molecules. Only recently, following ArQule's lead, has the drug-discovery community realized the power of Ugi's vision for quickly generating molecular diversity through robust, yet simple, reaction cascades that assemble multiple components in solution.
26. 2COOR').
27. We do not consider here the many polymerization (Ziegler-Natta) reactions of olefins and acetylenes and related processes, which account for the vast majority of man-made materials based on contiguous carbon - carbon bond networks. Being strongly exothermic and superbly efficient, these polymerizations are clearly based on click reactions, but ones which are hard to control for the construction of small molecules in the stepwise "modular" fashion of the reactions discussed above.
28. R. S. Bohacek, C. McMartin, W. C. Guida, Med. Res. Rev. 1996, 16, 3-50. K.B.S. thanks Prof. Daniel Rich for calling this paper to his attention during a visit to the University of Wisconsin in 1997.
29. 25 meters) or so: P. Morrison, P. Morrison, Powers of Ten, Scientific American, New York, 1982.
30. For further discussion of this approach, and its relation to process chemistry, see: Foreword by K. B. Sharpless in Practical Process Research & Development (Ed.: N. G. Anderson), Academic Press, San Diego, 2000.
31. 1. Other convenient comparisons, such as the ones shown in Scheme 1, can be made with the aid of the Benson group-additivity method: S. W. Benson, Thermochemical Kinetics, 2nd ed., Wiley, New York, 1976.
32. H. A. Wittcoff, B. G. Reuben in Industrial Organic Chemicals, Wiley, New York, 1996.
33. G. Wilke, A. Eckerle, Appl. Homogeneous Catal. Organomet. Compd. 1996, 1, 358-373;
34. b) P. W. Jolly. G. Wilke, The Organic Chemistry of Nickel, Vol. I and II, Academic Press, New York, 1975;
35. c) G. W. Parshall, W. A. Nugent, CHEMTECH 1988, 18, 314-320.
36. U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J. O. Metzger, M. Rüsch gen. Klaas, H. J. Schäfer, M. P. Schneider, Angew. Chem. 2000, 112, 2292-2310; Angew. Chem. Int. Ed. 2000, 39, 2206- 2224.
37. U. Biermann, W. Friedt, S. Lang, W. Lühs, G. Machmüller, J. O. Metzger, M. Rüsch gen. Klaas, H. J. Schäfer, M. P. Schneider, Angew. Chem. 2000, 112, 2292-2310; Angew. Chem. Int. Ed. 2000, 39, 2206-2224.
38. It should be appreciated that nature does make sparing use of olefin-based chemistries. In general, their high reactivity toward oxidation and addition makes olefins a liability for biology, in that harmful, irreversible reactions are possible. But occasionally, necessity seems to have been the mother of spectacular invention, as in the cationic cyclization of squalene epoxide to lanosterol. In this and related polyene cyclizations, we see that nature discovered the unique effectiveness of olefin oligomerization processes for turning unstable C=C networks into stable (C-C) ones some years before the petroleum chemist.
39. a) Tetrahedron 1998, 54(16) (special issue devoted to solution-phase combinatorial chemistry);
40. b) H. An, P. D. Cook, Chem. Rev. 2000, 100, 3311-3340.
41. For example, see: R. H. Griffey, H. An, L. L. Cummins, H. J. Gaus, B. Haly, R. Herrmann, P. D. Cook, Tetrahedron 1998, 54, 4067-4076.
42. a) C-J. Li, T.-H. Chan, Organic Reactions in Aqueous Media, Wiley, New York, 1997;
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44. c) Organic Synthesis in Water (Ed.: P. A. Grieco), Blackie, London, 1998;
45. d) R. Breslow, Acc. Chem. Res. 1991, 24, 159-164;
46. e) R. Breslow, Pure Appl. Chem. 1998, 70, 1933-1938.
47. J. J. Gajewski, Acc. Chem. Res. 1997, 30, 219-225.
48. See, for example: F. Fringuelli, O. Piermatti, F. Pizzo, L. Vaccaro, J. Org. Chem. 1999, 64, 6094-6096.
49. For an example of the beneficial effects of aqueous solvent on 1,3-dipolar cycloaddition reactions, see: D. van Mersbergen, J. W. Wijnen, J. B. F. N. Engberts, J. Org. Chem. 1998, 63, 8801-8805.
50. 1. The situation is more complicated when, as is often the case, either or both of the reaction components are poorly soluble in water.
51. Note, however, that amide bond synthesis by this or other methods, in spite of being strongly favorable thermodynamically, does not often reach the level of yield, generality, simplicity, and ease of product isolation that characterizes click reactions. For example, compare amide synthesis with the synthesis of ureas from amines and isocyanates. The latter process is a nearly perfect transformation, and like all the best click reactions it is a pure fusion process requiring no adjuvants of any kind. Amide bond formation, in contrast, usually requires external reagents and generates nontrivial by-products, factors contributing to uncertain outcomes in new circumstances. Reactions such as these are good enough for making building blocks, but not for the final assembly sequences.
52. A similar theme may be found in the development of sequential ("domino") reaction schemes for the rapid synthesis of single compounds or compound libraries. See, for example: L. F. Tietze, A. Modi. Med. Res. Rev. 2000, 20, 304-322; L. F. Tietze, M. E. Lieb, Curr. Opin. Chem. Biol. 1998, 2, 363-371; L. F. Tietze, Chem. Rev. 1996, 96, 115-136; L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137-170; Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163; A. Orita, Y. Nagano, K. Nakazawa, J. Otera, Synlett 2000, 599-602.
53. A similar theme may be found in the development of sequential ("domino") reaction schemes for the rapid synthesis of single compounds or compound libraries. See, for example: L. F. Tietze, A. Modi. Med. Res. Rev. 2000, 20, 304-322; L. F. Tietze, M. E. Lieb, Curr. Opin. Chem. Biol. 1998, 2, 363-371; L. F. Tietze, Chem. Rev. 1996, 96, 115-136; L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137-170; Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163; A. Orita, Y. Nagano, K. Nakazawa, J. Otera, Synlett 2000, 599-602.
54. A similar theme may be found in the development of sequential ("domino") reaction schemes for the rapid synthesis of single compounds or compound libraries. See, for example: L. F. Tietze, A. Modi. Med. Res. Rev. 2000, 20, 304-322; L. F. Tietze, M. E. Lieb, Curr. Opin. Chem. Biol. 1998, 2, 363-371; L. F. Tietze, Chem. Rev. 1996, 96, 115-136; L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137-170; Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163; A. Orita, Y. Nagano, K. Nakazawa, J. Otera, Synlett 2000, 599-602.
55. A similar theme may be found in the development of sequential ("domino") reaction schemes for the rapid synthesis of single compounds or compound libraries. See, for example: L. F. Tietze, A. Modi. Med. Res. Rev. 2000, 20, 304-322; L. F. Tietze, M. E. Lieb, Curr. Opin. Chem. Biol. 1998, 2, 363-371; L. F. Tietze, Chem. Rev. 1996, 96, 115-136; L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137-170; Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163; A. Orita, Y. Nagano, K. Nakazawa, J. Otera, Synlett 2000, 599-602.
56. A similar theme may be found in the development of sequential ("domino") reaction schemes for the rapid synthesis of single compounds or compound libraries. See, for example: L. F. Tietze, A. Modi. Med. Res. Rev. 2000, 20, 304-322; L. F. Tietze, M. E. Lieb, Curr. Opin. Chem. Biol. 1998, 2, 363-371; L. F. Tietze, Chem. Rev. 1996, 96, 115-136; L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137-170; Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163; A. Orita, Y. Nagano, K. Nakazawa, J. Otera, Synlett 2000, 599-602.
57. A similar theme may be found in the development of sequential ("domino") reaction schemes for the rapid synthesis of single compounds or compound libraries. See, for example: L. F. Tietze, A. Modi. Med. Res. Rev. 2000, 20, 304-322; L. F. Tietze, M. E. Lieb, Curr. Opin. Chem. Biol. 1998, 2, 363-371; L. F. Tietze, Chem. Rev. 1996, 96, 115-136; L. F. Tietze, U. Beifuss, Angew. Chem. 1993, 105, 137-170; Angew. Chem. Int. Ed. Engl. 1993, 32, 131-163; A. Orita, Y. Nagano, K. Nakazawa, J. Otera, Synlett 2000, 599-602.
58. The series Houben-Weyl: Methods of Organic Chemistry, Thieme Verlag, Stuttgart remains unchallenged as the best source of information of this type.
59. a) J. I. Crowley, H. Rapoport, Acc. Chem. Res. 1976, 9, 135-144;
60. b) J. S. Früchtel, G. Jung, Angew. Chem. 1996, 108, 19-46; Angew. Chem. Int. Ed. Engt. 1996, 35, 17-42;
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64. Aziridination: a) J. U. Jeong, B. Tao, I. Sagasser, H. Henniges, K. B. Sharpless, J. Am. Chem. Soc. 1998, 120, 6844-6845; b) A. V. Gontcharov, H. Liu, K. B. Sharpless, Org. Lett. 1999, 1, 783-786.
65. Aziridination: a) J. U. Jeong, B. Tao, I. Sagasser, H. Henniges, K. B. Sharpless, J. Am. Chem. Soc. 1998, 120, 6844-6845; b) A. V. Gontcharov, H. Liu, K. B. Sharpless, Org. Lett. 1999, 1, 783-786.
66. Olefin epoxidation using methylrhenium trioxide as a catalyst in the presence of amine additives: a) H. Adolfsson, A. Converso, K. B. Sharpless, Tetrahedron Lett. 1999, 40, 3991-3994; b) W. A. Herrmann, R. W. Fischer, D. W. Marz, Angew. Chem. Int. Ed. Engl. 1991, 30, 1638-1641; c) W. A. Herrmann, F. E. Kühn, Acc. Chem. Res. 1997, 30, 169-180; d) J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, J. Am. Chem. Soc. 1997, 119, 6189-6190.
67. Olefin epoxidation using methylrhenium trioxide as a catalyst in the presence of amine additives: a) H. Adolfsson, A. Converso, K. B. Sharpless, Tetrahedron Lett. 1999, 40, 3991-3994; b) W. A. Herrmann, R. W. Fischer, D. W. Marz, Angew. Chem. Int. Ed. Engl. 1991, 30, 1638-1641; c) W. A. Herrmann, F. E. Kühn, Acc. Chem. Res. 1997, 30, 169-180; d) J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, J. Am. Chem. Soc. 1997, 119, 6189-6190.
68. Olefin epoxidation using methylrhenium trioxide as a catalyst in the presence of amine additives: a) H. Adolfsson, A. Converso, K. B. Sharpless, Tetrahedron Lett. 1999, 40, 3991-3994; b) W. A. Herrmann, R. W. Fischer, D. W. Marz, Angew. Chem. Int. Ed. Engl. 1991, 30, 1638-1641; c) W. A. Herrmann, F. E. Kühn, Acc. Chem. Res. 1997, 30, 169-180; d) J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, J. Am. Chem. Soc. 1997, 119, 6189-6190.
69. Olefin epoxidation using methylrhenium trioxide as a catalyst in the presence of amine additives: a) H. Adolfsson, A. Converso, K. B. Sharpless, Tetrahedron Lett. 1999, 40, 3991-3994; b) W. A. Herrmann, R. W. Fischer, D. W. Marz, Angew. Chem. Int. Ed. Engl. 1991, 30, 1638-1641; c) W. A. Herrmann, F. E. Kühn, Acc. Chem. Res. 1997, 30, 169-180; d) J. Rudolph, K. L. Reddy, J. P. Chiang, K. B. Sharpless, J. Am. Chem. Soc. 1997, 119, 6189-6190.
70. Reviews of the asymmetric epoxidation of allylic alcohols: a) T. Katsuki, V. S. Martin, Org. React. 1996, 48, 1-299; b) R. A. Johnson, K. B. Sharpless in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, New York, 1993, pp. 101-158.
71. Reviews of the asymmetric epoxidation of allylic alcohols: a) T. Katsuki, V. S. Martin, Org. React. 1996, 48, 1-299; b) R. A. Johnson, K. B. Sharpless in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, New York, 1993, pp. 101-158.
72. Reviews of the asymmetric epoxidation of unfunctionalized olefins: a) T. Katsuki, J. Mol. Catal. A 1996, 113, 87-107; b) E. N. Jacobsen, in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, New York, 1993, pp. 159-202.
73. Reviews of the asymmetric epoxidation of unfunctionalized olefins: a) T. Katsuki, J. Mol. Catal. A 1996, 113, 87-107; b) E. N. Jacobsen, in Catalytic Asymmetric Synthesis (Ed.: I. Ojima), VCH, New York, 1993, pp. 159-202.
74. Osmium-catalyzed dihydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless. Transition Met Org. Synth. 1998, 2, 219-242; b) H. C. Kolb, M. VanNieuwenhze, K. B. Sharpless, Chem. Rev. 1994, 94, 2483- 2547.
75. Osmium-catalyzed dihydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless. Transition Met Org. Synth. 1998, 2, 219-242; b) H. C. Kolb, M. VanNieuwenhze, K. B. Sharpless, Chem. Rev. 1994, 94, 2483-2547.
76. Review of the osmium-catalyzed aminohydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless, Transition Met. Org. Synth. 1998, 2, 243-260; b) G. Schlingoff, K. B. Sharpless in Asymmetric Oxidations Reactions: A Practical Approach (Ed.: T. Katsuki), Oxford University Press, in press; use of amino-substituted heterocycles as nitrogen source: L. J. Goossen, H. Liu, K. R. Dress, K. B. Sharpless, Angew. Chem. 1999, 111, 1149-1152; Angew. Chem. Int. Ed. Engl. 1999, 38, 1080-1083; K. R. Dress, L. J. Goossen, H. Liu, D. M. Jerina, K. B. Sharpless, Tetrahedron Lett. 1998, 39, 7669-7672; d) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221-2223.
77. Review of the osmium-catalyzed aminohydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless, Transition Met. Org. Synth. 1998, 2, 243-260; b) G. Schlingoff, K. B. Sharpless in Asymmetric Oxidations Reactions: A Practical Approach (Ed.: T. Katsuki), Oxford University Press, in press; use of amino-substituted heterocycles as nitrogen source: L. J. Goossen, H. Liu, K. R. Dress, K. B. Sharpless, Angew. Chem. 1999, 111, 1149-1152; Angew. Chem. Int. Ed. Engl. 1999, 38, 1080-1083; K. R. Dress, L. J. Goossen, H. Liu, D. M. Jerina, K. B. Sharpless, Tetrahedron Lett. 1998, 39, 7669-7672; d) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221-2223.
78. Review of the osmium-catalyzed aminohydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless, Transition Met. Org. Synth. 1998, 2, 243-260; b) G. Schlingoff, K. B. Sharpless in Asymmetric Oxidations Reactions: A Practical Approach (Ed.: T. Katsuki), Oxford University Press, in press; use of amino-substituted heterocycles as nitrogen source: L. J. Goossen, H. Liu, K. R. Dress, K. B. Sharpless, Angew. Chem. 1999, 111, 1149-1152; Angew. Chem. Int. Ed. Engl. 1999, 38, 1080-1083; K. R. Dress, L. J. Goossen, H. Liu, D. M. Jerina, K. B. Sharpless, Tetrahedron Lett. 1998, 39, 7669-7672; d) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221-2223.
79. Review of the osmium-catalyzed aminohydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless, Transition Met. Org. Synth. 1998, 2, 243-260; b) G. Schlingoff, K. B. Sharpless in Asymmetric Oxidations Reactions: A Practical Approach (Ed.: T. Katsuki), Oxford University Press, in press; use of amino-substituted heterocycles as nitrogen source: L. J. Goossen, H. Liu, K. R. Dress, K. B. Sharpless, Angew. Chem. 1999, 111, 1149-1152; Angew. Chem. Int. Ed. Engl. 1999, 38, 1080-1083; K. R. Dress, L. J. Goossen, H. Liu, D. M. Jerina, K. B. Sharpless, Tetrahedron Lett. 1998, 39, 7669-7672; d) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221-2223.
80. Review of the osmium-catalyzed aminohydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless, Transition Met. Org. Synth. 1998, 2, 243-260; b) G. Schlingoff, K. B. Sharpless in Asymmetric Oxidations Reactions: A Practical Approach (Ed.: T. Katsuki), Oxford University Press, in press; use of amino-substituted heterocycles as nitrogen source: L. J. Goossen, H. Liu, K. R. Dress, K. B. Sharpless, Angew. Chem. 1999, 111, 1149-1152; Angew. Chem. Int. Ed. Engl. 1999, 38, 1080-1083; K. R. Dress, L. J. Goossen, H. Liu, D. M. Jerina, K. B. Sharpless, Tetrahedron Lett. 1998, 39, 7669-7672; d) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221-2223.
81. Review of the osmium-catalyzed aminohydroxylation of olefins: a) H. C. Kolb, K. B. Sharpless, Transition Met. Org. Synth. 1998, 2, 243-260; b) G. Schlingoff, K. B. Sharpless in Asymmetric Oxidations Reactions: A Practical Approach (Ed.: T. Katsuki), Oxford University Press, in press; use of amino-substituted heterocycles as nitrogen source: L. J. Goossen, H. Liu, K. R. Dress, K. B. Sharpless, Angew. Chem. 1999, 111, 1149-1152; Angew. Chem. Int. Ed. Engl. 1999, 38, 1080-1083; K. R. Dress, L. J. Goossen, H. Liu, D. M. Jerina, K. B. Sharpless, Tetrahedron Lett. 1998, 39, 7669-7672; d) Z. P. Demko, M. Bartsch, K. B. Sharpless, Org. Lett. 2000, 2, 2221-2223.
82. For a recent review of the asymmetric synthesis of aziridines from amino alcohols, epoxides, alkenes, and imines, see: H. M. I. Osborn, J. Sweeney, Tetrahedron: Asymmetry 1997, 8, 1693-1715.
83. a) A. E. Rubin, K. B. Sharpless, Angew. Chem. 1997, 109, 2751-2754; Angew. Chem. Int. Ed. Engl. 1997, 36, 2637-2640;
84. a) A. E. Rubin, K. B. Sharpless, Angew. Chem. 1997, 109, 2751-2754; Angew. Chem. Int. Ed. Engl. 1997, 36, 2637-2640;
85. b) W. C. Pringle, K. B. Sharpless, unpublished results;
86. c) V. V. Fokin, K. B. Sharpless, Angew. Chem., in press; Angew. Chem. Int. Ed., in press;
87. c) V. V. Fokin, K. B. Sharpless, Angew. Chem., in press; Angew. Chem. Int. Ed., in press;
88. d) see also: W. Pringle, K. B. Sharpless, Tetrahedron Lett. 1999, 40, 5151-5154.
89. For an appreciation of the virtues of fusion processes from the viewpoint of "atom economy", see: B. M. Trost, Science 1991, 254, 1471-1477.
90. a) The fact that stereoelectronic factors disfavor eliminations in small rings has allowed the stereoselective alkylalion of the α-carbon of carboxylic acids, with oxygen-containing functionality in the β-position, through heterocyclic enolates with an exocyclic double bond (D. Seebach. J. D. Aebi, M. Gander-Coquoz, R. Naef, Helv. Chim. Acta 1987, 70, 1194-1216). For other uses of oxiranyl anions, see:
91. b) T. Satoh, Chem. Rev. 1996, 96, 3303-3325;
92. c) Y. Mori, Rev. Heteroat. Chem. 1997, 17, 183-211;
93. d) T. Satoh, S. Kobayashi, S. Nakanishi, K. Horiguchi, S. Irisa, Tetrahedron 1999, 55, 2515-2528;
94. e) Y. Mori, K. Yaegashi, H. Furukawa, J. Am. Chem. Soc. 1997, 119, 4557-4558.
95. Care must be exercised with these reactive electrophiles, since the ring-opening reactions are exothermic and often autocatalytic when performed neat with basic amines as the nucleophile. In large-scale applications without solvent, it is essential to start at a temperature where the reaction at hand has been shown to be self-sustaining and the amines then added at a rate to maintain the desired temperature. If water alone cannot be used as solvent, we often employ boiling n-propanol or boiling toluene for large-scale applications (depending on whether or not a protic or aprotic environment is desired (see refs. [44b] and [45]); in the former case, the addition of water after cooling often results in precipitation of the product.
96. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456- 461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
97. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456- 461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
98. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456-461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
99. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456- 461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
100. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456- 461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
101. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456- 461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
102. Synthesis of cis-1,4-cyclohexadiene epoxides: a) T. W. Craig, G. R. Harvey, G. A. Berchtold, J. Org. Chem. 1967, 32, 3743-3749; b) G. Kavadias. S. Velkof, B. Belleau, Can. J. Chem. 1978, 56, 404-409; c) T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456- 461; for ring-opening reactions of six-membered ring di- and triepoxides, see: d) R. Kuehlmeyer, R. Keller, R. Schwesinger, T. Netscher, H. Fritz, H. Prinzbach, Chem. Ber. 1984, 117, 1765-1800; e) J. Schubert. R. Keller, R. Schwesinger, H. Prinzbach, Chem. Ber. 1983, 116, 2524-2545; f) C. Rucker, H. Muller-Botticher, W. D. Braschwitz, H. Prinzbach, U. Reifenstahl, H. Irngartinger, Liebigs Ann. 1997, 967-989; g) S. Kagabu, C. Kaiser, R. Keller, P. G. Becker, K. H. Mueller, L. Knothe, G. Rihs, H. Prinzbach, Chem. Ber. 1988, 121, 741-756.
103. a) H. T. Chang, J. P. Chiang, K. L. Reddy, M. A. Winter, A. K. Yudin, K. B. Sharpless, unpublished results;
104. b) for previous studies on the regioselectivity of the ring opening of cis- and trans-1,4-cyclohexadiene diepoxides, see: G. Kavadias, R. Droghini, Can. J. Chem. 1979, 57, 1870- 1876; F. Haviv, B. Belleau, Can. J. Chem. 1978, 56, 2677- 2680; T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456-461.
105. b) for previous studies on the regioselectivity of the ring opening of cis- and trans-1,4-cyclohexadiene diepoxides, see: G. Kavadias, R. Droghini, Can. J. Chem. 1979, 57, 1870- 1876; F. Haviv, B. Belleau, Can. J. Chem. 1978, 56, 2677-2680; T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456-461.
106. b) for previous studies on the regioselectivity of the ring opening of cis- and trans-1,4-cyclohexadiene diepoxides, see: G. Kavadias, R. Droghini, Can. J. Chem. 1979, 57, 1870- 1876; F. Haviv, B. Belleau, Can. J. Chem. 1978, 56, 2677- 2680; T. Suami, S. Ogawa, H. Uchino, Y. Funaki, J. Org. Chem. 1975, 40, 456-461.
107. The 1,3-selectivity in the neat reaction (that is, 1→2) probably stems from the interplay of two effects: trans-diaxial epoxide opening and intramolecular epoxide activation by the hydroxy group that is released in the first step (see Scheme 19). The latter effect is much less important in the presence of a protic solvent, and thereby allows the intermediate hydroxy epoxide to react from the other, more stable chair conformer, which gives rise to the diamine from 1.4-attack (that is, 1→3, Scheme 7). matrix presented Scheme 19.
108. For the nucleophilic opening of epoxides derived from tetrahydronaphthalene and hexahydroanthracene, see: a) E. Vogel, F. Kuebart, J. A. Marco, R. Andree, J. Am. Chem. Soc. 1983, 105, 6982-6983; b) E. Vogel, W. Klug, A. Breuer, Org. Synth. Coll. Vol. 1988, 6, 862- 865; c) E. Vogel, M. Biskup, A. Vogel, H. Günther, Angew. Chem. 1966, 78, 755-756; Angew. Chem. Int. Ed. Engl. 1966, 5, 734-735; d) A. K. Yudin, J. P. Chiang, K. B. Sharpless, unpublished results.
109. For the nucleophilic opening of epoxides derived from tetrahydronaphthalene and hexahydroanthracene, see: a) E. Vogel, F. Kuebart, J. A. Marco, R. Andree, J. Am. Chem. Soc. 1983, 105, 6982-6983; b) E. Vogel, W. Klug, A. Breuer, Org. Synth. Coll. Vol. 1988, 6, 862-865; c) E. Vogel, M. Biskup, A. Vogel, H. Günther, Angew. Chem. 1966, 78, 755-756; Angew. Chem. Int. Ed. Engl. 1966, 5, 734-735; d) A. K. Yudin, J. P. Chiang, K. B. Sharpless, unpublished results.
110. For the nucleophilic opening of epoxides derived from tetrahydronaphthalene and hexahydroanthracene, see: a) E. Vogel, F. Kuebart, J. A. Marco, R. Andree, J. Am. Chem. Soc. 1983, 105, 6982-6983; b) E. Vogel, W. Klug, A. Breuer, Org. Synth. Coll. Vol. 1988, 6, 862- 865; c) E. Vogel, M. Biskup, A. Vogel, H. Günther, Angew. Chem. 1966, 78, 755-756; Angew. Chem. Int. Ed. Engl. 1966, 5, 734-735; d) A. K. Yudin, J. P. Chiang, K. B. Sharpless, unpublished results.
111. For the nucleophilic opening of epoxides derived from tetrahydronaphthalene and hexahydroanthracene, see: a) E. Vogel, F. Kuebart, J. A. Marco, R. Andree, J. Am. Chem. Soc. 1983, 105, 6982-6983; b) E. Vogel, W. Klug, A. Breuer, Org. Synth. Coll. Vol. 1988, 6, 862- 865; c) E. Vogel, M. Biskup, A. Vogel, H. Günther, Angew. Chem. 1966, 78, 755-756; Angew. Chem. Int. Ed. Engl. 1966, 5, 734-735; d) A. K. Yudin, J. P. Chiang, K. B. Sharpless, unpublished results.
112. For the nucleophilic opening of epoxides derived from tetrahydronaphthalene and hexahydroanthracene, see: a) E. Vogel, F. Kuebart, J. A. Marco, R. Andree, J. Am. Chem. Soc. 1983, 105, 6982-6983; b) E. Vogel, W. Klug, A. Breuer, Org. Synth. Coll. Vol. 1988, 6, 862- 865; c) E. Vogel, M. Biskup, A. Vogel, H. Günther, Angew. Chem. 1966, 78, 755-756; Angew. Chem. Int. Ed. Engl. 1966, 5, 734-735; d) A. K. Yudin, J. P. Chiang, K. B. Sharpless, unpublished results.
113. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
114. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951-1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
115. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
116. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
117. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
118. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
119. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
120. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
121. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326-5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
122. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
123. See ref. [33a]; synthesis by transition metal catalyzed aziridination of olefins, see: H. Kwart, A. A. Kahn, J. Am. Chem. Soc. 1967, 89, 1951- 1953; D. Mansury, J.-P. Mahy, D. Annie, B. Gustave, P. Battioni, J. Chem. Soc. Chem. Commun. 1984, 1161-1163; D. A. Evans, M. M. Faul, M. T. Bilodeau, J. Org. Chem. 1991, 56, 6744-6746; E. Vedejs, H. Sano, Tetrahedron Lett. 1992, 33, 3261-3264; M. J. Sodergren, D. A. Alonso. A. V. Bedekar, P. G. Andersson, Tetrahedron Lett. 1997, 38, 6897-6900; asymmetric transition metal catalyzed aziridination of olefins: D. A. Evans, M. M. Faul, M. T. Bilodeau, B. A. Anderson, D. M. Barnes, J. Am. Chem. Soc. 1993, 115, 5328-5329; R. E. Rowenthal, S. Masamune, Tetrahedron Lett. 1991, 32, 7373-7376; Z. Li, K. B. Conser, E. N. Jacobson, J. Am. Chem. Soc. 1993, 115, 5326- 5327; H. Nishikori, T. Katsuki, Tetrahedron Lett. 1996, 37, 9245-9248; aziridination of olefins with PhI=NTs: Y. Yamada, T. Yamamoto, Chem. Lett. 1975, 361.
124. a) D. Tanner, C. Birgersson, Tetrahedron Lett. 1991, 32, 2533-2536;
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139. For a study on the influence of Lewis acids on the nucleophilic opening of N-acyl aziridines versus their rearrangement to oxazolines, see: D. Ferraris, W. J. Drury III, C. Cox, T. Lectka, J. Org. Chem. 1998, 63, 4568-4569.
140. a) H. Stamm, J. Prakt. Chem. 1999, 341, 319-331;
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144. See, for example: a) D. Tanner, Angew. Chem. 1994, 106, 625-646; Angew. Chem. Int. Ed. Engl. 1994, 33, 599-619; b) Y. L. Bennani, G.- D. Zhu, J. C. Freeman, Synlett 1998, 754-756.
145. See, for example: a) D. Tanner, Angew. Chem. 1994, 106, 625-646; Angew. Chem. Int. Ed. Engl. 1994, 33, 599-619; b) Y. L. Bennani, G.-D. Zhu, J. C. Freeman, Synlett 1998, 754-756.
146. H.-T. Chang, Z. Chen, H. C. Kolb, K. B. Sharpless, unpublished results.
147. Opening of aziridines with thiols, see:a) G. Meguerian, L. B. Clapp, J. Am. Chem. Soc. 1951, 73, 2121-2124; b) J. Legters, L. Thijs, B. Zwanenburg, Recl. Trav. Chim. Pays-Bas 1992, 111, 1-15; c) H. Shao, O. Zhu, M. Goodman, J. Org. Chem. 1995, 60, 790-791.
148. Opening of aziridines with thiols, see:a) G. Meguerian, L. B. Clapp, J. Am. Chem. Soc. 1951, 73, 2121-2124; b) J. Legters, L. Thijs, B. Zwanenburg, Recl. Trav. Chim. Pays-Bas 1992, 111, 1-15; c) H. Shao, O. Zhu, M. Goodman, J. Org. Chem. 1995, 60, 790-791.
149. Opening of aziridines with thiols, see:a) G. Meguerian, L. B. Clapp, J. Am. Chem. Soc. 1951, 73, 2121-2124; b) J. Legters, L. Thijs, B. Zwanenburg, Recl. Trav. Chim. Pays-Bas 1992, 111, 1-15; c) H. Shao, O. Zhu, M. Goodman, J. Org. Chem. 1995, 60, 790-791.
150. a) Z.-M. Wang, J. E. Pease, K. R. Dress, K. B. Sharpless, unpublished results;
151. b) WARNING: When the neat synthesis of 7 (Scheme 9) was performed on a 3-gram scale, it took off with a "pop" and most of the white crystalline product ended up on the ceiling of the fume hood. The autocatalysis mentioned in ref. [43] is especially dramatic in such neat amine openings of N-sulfonylaziridines, since the newly created sulfonamide N-H bond, being almost
152. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
153. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
154. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
155. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
156. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
157. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
158. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
159. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
160. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
161. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
162. For selected examples, see: a) S. E. De Sousa, P. O'Brien, P. Poumellec, J. Chem. Soc. Perkin Trans. 1 1998, 1483-1492; b) P. A. Grieco, W. A. Carroll, Tetrahedron Lett. 1992, 33, 4401-4404; c) S. V. D'Andrea, E. T. Michalson, J. P. Freeman, C. G. Chidester. J. Szmuszkovicz, J. Org. Chem. 1991, 56, 3133-3137; d) P. Gmeiner, Heterocycles 1991, 32, 1499-1504; e) R. K. Dieter, N. Deo, B. Lagu, J. W. Dieter, J. Org. Chem. 1992, 57, 1663-1671; f) S. Zhao, J. P. Freeman, C. G. Chidester, P. F. von Voigtlander, S. A. Mizsak, J. Szmuszkovicz, J. Org. Chem. 1993, 58, 4043-4048; g) H. H. Wasserman, C. B. Vu, Tetrahedron Lett. 1994, 35, 9779-9782; h) S. Zhao, A. Ghosh, S. V. D'Andrea, J. P. Freeman, P. F. von Voigtlander, D. B. Carter, M. W. Smith, J. R. Blinn, J. Szmuszkovicz, Heterocycles 1994, 39, 163-170; i) D.-K. Kim, G. Kim, Y.-W. Kim, J. Chem. Soc. Perkin Trans. 1 1996, 803-808; j) G. Miao, B. E. Rossiter, J. S. Bradshaw. J. Org. Chem. 1995, 60, 8424-8427; k) C. Perrio-Huard, C. Ducandas, M. C. Lasne, B. Moreau, J. Chem. Soc. Perkin Trans. 1 1996, 2925-2932.
163. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
164. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
165. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
166. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
167. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
168. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
169. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
170. For selected examples, see: a) T. R. Webb, C. Eigenbrot, J. Org. Chem. 1991, 56, 3009-3016; b) M. Shrimali, R. Kalsi, S. S. Parmar, J. P. Barthwal, Arzneim. Forsch. 1991, 41, 101-103; c) S. Corsano, G. Strappaghetti, A. Codagnone, R. Scapicchi, G. Marucci, Eur. J. Med. Chem. 1992, 27, 545-549; d) M. A. Williams, H. Rapoport, J. Org. Chem. 1994, 59, 3616-3625; e) T. Morie, S. Kato, H. Harada, I. Fujiwara, K. Watanabe, J. Matsumoto, J. Chem. Soc. Perkin Trans. 1 1994, 2565-2569; f) S. Corsano, G. Strappaghetti, R. Scapicchi, G. Marucci, Arch. Pharm. 1996, 329, 468-470; g) E. J. Corey, R. Naef, F.J. Hannon, J. Am. Chem. Soc. 1986, 108, 7114-7116; h) L. F. Lindoy, B. W. Skelton, S. V. Smith, A. H. White, Aust. J. Chem. 1993, 46, 363-375.
171. P.F. Richardson, L. T. J. Nelson, K. B. Sharpless, Tetrahedron Lett. 1995, 36, 9241-9244.
172. a) J. A. J. M. Vincent, P. Schipper, A. deGroot, H. M. Buck, Tetrahedron Lett. 1975, 1989-1992;
173. b) W. H. Mueller, Angew. Chem. 1969, 81, 475-484; Angew. Chem. Int. Ed. Engl. 1969, 8, 482-492.
174. b) W. H. Mueller, Angew. Chem. 1969, 81, 475-484; Angew. Chem. Int. Ed. Engl. 1969, 8, 482-492.
175. K. Burow, B. Tao, A. Converso, M. G. Finn, K. B. Sharpless, unpublished results.
176. T.-H. Chuang, K. B. Sharpless, Org. Lett. 1999, 1, 1435-1437.
177. T.-H. Chuang, A. Converso, K. Burow, K. L. Reddy, A. Marzinzik, K. B. Sharpless, unpublished results.
178. For a review, see: E. Kühle, Synthesis 1971, 563-586.
179. a) For a review, see: M. Mühlstädt, D. Martinetz, Z. Chem. 1974, 14, 297-304;
180. 2: M. Mühlstädt, M. Ecke, K. Hollmann, M. Möder, DE-B 288 603 A5, 1983;
181. 2 to cycloheptadienones: P. H. McCabe, W. Routledge, Tetrahedron Lett. 1976, 85-86;
182. d) reaction with aryl allyl ethers: M. Mühlstädt, K. Hollmann, R. Widera, Tetrahedron Lett. 1983, 24, 3203-3204; reaction with acyclic non- conjugated dienes: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2620- 2627;
183. d) reaction with aryl allyl ethers: M. Mühlstädt, K. Hollmann, R. Widera, Tetrahedron Lett. 1983, 24, 3203-3204; reaction with acyclic non-conjugated dienes: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2620-2627;
184. e) reaction with cyclic polyolefins: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2627-2633; F. Lautenschlaeger, Chemistry in Sulfides Conference (Ed.: A. V. Tobolsky), Interscience, New York, 1968, pp. 73-81; E. D. Weil, K. J. Smith, R. J. Gruber, J. Org. Chem. 1966, 31, 1669-1679; F. Lautenschlaeger, J. Org. Chem. 1966, 31, 1679; E. J. Corey, E. Block, J. Org. Chem. 1966, 31, 1663-1668; F. Lautenschlaeger, Can. J. Chem. 1966, 44, 2813-2817;
185. e) reaction with cyclic polyolefins: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2627-2633; F. Lautenschlaeger, Chemistry in Sulfides Conference (Ed.: A. V. Tobolsky), Interscience, New York, 1968, pp. 73-81; E. D. Weil, K. J. Smith, R. J. Gruber, J. Org. Chem. 1966, 31, 1669-1679; F. Lautenschlaeger, J. Org. Chem. 1966, 31, 1679; E. J. Corey, E. Block, J. Org. Chem. 1966, 31, 1663-1668; F. Lautenschlaeger, Can. J. Chem. 1966, 44, 2813-2817;
186. e) reaction with cyclic polyolefins: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2627-2633; F. Lautenschlaeger, Chemistry in Sulfides Conference (Ed.: A. V. Tobolsky), Interscience, New York, 1968, pp. 73-81; E. D. Weil, K. J. Smith, R. J. Gruber, J. Org. Chem. 1966, 31, 1669-1679; F. Lautenschlaeger, J. Org. Chem. 1966, 31, 1679; E. J. Corey, E. Block, J. Org. Chem. 1966, 31, 1663-1668; F. Lautenschlaeger, Can. J. Chem. 1966, 44, 2813-2817;
187. e) reaction with cyclic polyolefins: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2627-2633; F. Lautenschlaeger, Chemistry in Sulfides Conference (Ed.: A. V. Tobolsky), Interscience, New York, 1968, pp. 73-81; E. D. Weil, K. J. Smith, R. J. Gruber, J. Org. Chem. 1966, 31, 1669-1679; F. Lautenschlaeger, J. Org. Chem. 1966, 31, 1679; E. J. Corey, E. Block, J. Org. Chem. 1966, 31, 1663-1668; F. Lautenschlaeger, Can. J. Chem. 1966, 44, 2813-2817;
188. e) reaction with cyclic polyolefins: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2627-2633; F. Lautenschlaeger, Chemistry in Sulfides Conference (Ed.: A. V. Tobolsky), Interscience, New York, 1968, pp. 73-81; E. D. Weil, K. J. Smith, R. J. Gruber, J. Org. Chem. 1966, 31, 1669-1679; F. Lautenschlaeger, J. Org. Chem. 1966, 31, 1679; E. J. Corey, E. Block, J. Org. Chem. 1966, 31, 1663-1668; F. Lautenschlaeger, Can. J. Chem. 1966, 44, 2813-2817;
189. e) reaction with cyclic polyolefins: F. Lautenschlaeger, J. Org. Chem. 1968, 33, 2627-2633; F. Lautenschlaeger, Chemistry in Sulfides Conference (Ed.: A. V. Tobolsky), Interscience, New York, 1968, pp. 73-81; E. D. Weil, K. J. Smith, R. J. Gruber, J. Org. Chem. 1966, 31, 1669-1679; F. Lautenschlaeger, J. Org. Chem. 1966, 31, 1679; E. J. Corey, E. Block, J. Org. Chem. 1966, 31, 1663-1668; F. Lautenschlaeger, Can. J. Chem. 1966, 44, 2813-2817;
190. f) reaction with vinyl cyclohexenes: G. A. Tolstikov, B. M. Lerman, N. G. Komissarova, L. M. Zelenova, Zh. Org. Khim. 1983, 19, 321-332; G. A. Tolstikov, B. M. Lerman, N. G. Komissarova, Zh. Org. Khim. 1983, 19, 299-310.
191. f) reaction with vinyl cyclohexenes: G. A. Tolstikov, B. M. Lerman, N. G. Komissarova, L. M. Zelenova, Zh. Org. Khim. 1983, 19, 321-332; G. A. Tolstikov, B. M. Lerman, N. G. Komissarova, Zh. Org. Khim. 1983, 19, 299-310.
192. A. Converso, A. Marzinzik, A. R. Vaino, K. Burow, K. P. M. VanHessche, H. C. Kolb, M. G. Finn, K. B. Sharpless, unpublished results.
193. A. Converso, K. Burow, A. Marzinzik, K. B. Sharpless, M. G. Finn, J. Org. Chem., in press.
194. For a review of the use of the hetero-Diels-Alder reaction in organic chemistry, see: L. F. Tietze, G. Kettschau. Top. Curr. Chem. 1997, 189, 1-120.
195. For a review of the asymmetric hetero-Diels-Alder reaction, see: H. Waldmann, Synthesis 1994, 535-551.
196. a) R. Huisgen in 1,3-Dipolar Cycloaddition Chemistry (Ed.: A. Padwa), Wiley, New York, 1984, pp. 1-176;
197. b) A. Padwa in Comprehensive Organic Synthesis, Vol. 4 (Ed.: B. M. Trost), Pergamon, Oxford, 1991, pp. 1069-1109.
198. For a review of asymmetric 1,3-dipolar cycloaddition reactions, see: K. V. Gothelf, K. A. Jorgensen, Chem. Rev. 1998, 98, 863-909.
199. For a review of synthetic applications, see: J. Mulzer, Org. Synth. Highlights 1991, 77-95.
200. a) W.-Q. Fan, A. R. Katritzky in Comprehensive Heterocyclic Chemistry II, Vol. 4 (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford, 1996, pp. 101-126;
201. b) R. N. Butler in Comprehensive Heterocyclic Chemistry II, Vol. 4 (Eds.: A. R. Katritzky, C. W. Rees, E. F. V. Scriven), Pergamon, Oxford, 1996, pp. 621-678;
202. c) K. Banert, Chem. Ber. 1989, 122, 911-918.
203. a) R. Huisgen, Pure Appl. Chem. 1989, 61, 613-628;
204. b) R. Huisgen, G. Szeimies, L. Moebius, Chem. Ber. 1967, 100, 2494-2507;
205. c) W. Lwowski in 1,3-Dipolar Cycloaddition Chemistry, Vol. 1 (Ed.: A. Padwa), Wiley, New York, 1984, Chap. 5:
206. d) J. Bastide, J. Hamelin. F. Texier, V. O. Ven, Bull. Soc. Chim. Fr. 1973, 2555-2579; J. Bastide, J. Hamelin, F. Texier, V. Q. Ven, Bull. Soc. Chim. Fr. 1973, 2871-2887.
207. d) J. Bastide, J. Hamelin. F. Texier, V. O. Ven, Bull. Soc. Chim. Fr. 1973, 2555-2579; J. Bastide, J. Hamelin, F. Texier, V. Q. Ven, Bull. Soc. Chim. Fr. 1973, 2871-2887.
208. -1, respectively). For these reasons, azides should not be distilled or treated in a careless fashion. However, when common sense is employed, they can be prepared, stored, and used without risk in the standard organic chemistry laboratory: We have never experienced a safety problem with these materials. See: M. Peer, Spec. Chem. 1998, 18, 256-263.
209. Recent examples of the use of this process include: a) M. Yamashita, K. Suzuki, Y. Kato, A. Iida, K. Ikai, P. M. Reddy, T. Oshikawa, J. Carbohydr. Chem. 1999, 18, 915-935; b) M. Moore, P. Norris, Tetrahedron Lett. 1998, 39, 7027-7030; c) D. J. Hlasta, J. H. Ackerman, J. Org. Chem. 1994, 59, 6184-6189; d) F. Palacios, A. M. Ochoa de Retana, J. Pagalday, Heterocyctes 1994, 38, 95-102; e) W. H. Pearson, S. C. Bergmeier, J. A. Chytra, Synthesis 1990, 156-159.
210. Recent examples of the use of this process include: a) M. Yamashita, K. Suzuki, Y. Kato, A. Iida, K. Ikai, P. M. Reddy, T. Oshikawa, J. Carbohydr. Chem. 1999, 18, 915-935; b) M. Moore, P. Norris, Tetrahedron Lett. 1998, 39, 7027-7030; c) D. J. Hlasta, J. H. Ackerman, J. Org. Chem. 1994, 59, 6184-6189; d) F. Palacios, A. M. Ochoa de Retana, J. Pagalday, Heterocyctes 1994, 38, 95-102; e) W. H. Pearson, S. C. Bergmeier, J. A. Chytra, Synthesis 1990, 156-159.
211. Recent examples of the use of this process include: a) M. Yamashita, K. Suzuki, Y. Kato, A. Iida, K. Ikai, P. M. Reddy, T. Oshikawa, J. Carbohydr. Chem. 1999, 18, 915-935; b) M. Moore, P. Norris, Tetrahedron Lett. 1998, 39, 7027-7030; c) D. J. Hlasta, J. H. Ackerman, J. Org. Chem. 1994, 59, 6184-6189; d) F. Palacios, A. M. Ochoa de Retana, J. Pagalday, Heterocyctes 1994, 38, 95-102; e) W. H. Pearson, S. C. Bergmeier, J. A. Chytra, Synthesis 1990, 156-159.
212. Recent examples of the use of this process include: a) M. Yamashita, K. Suzuki, Y. Kato, A. Iida, K. Ikai, P. M. Reddy, T. Oshikawa, J. Carbohydr. Chem. 1999, 18, 915-935; b) M. Moore, P. Norris, Tetrahedron Lett. 1998, 39, 7027-7030; c) D. J. Hlasta, J. H. Ackerman, J. Org. Chem. 1994, 59, 6184-6189; d) F. Palacios, A. M. Ochoa de Retana, J. Pagalday, Heterocyctes 1994, 38, 95-102; e) W. H. Pearson, S. C. Bergmeier, J. A. Chytra, Synthesis 1990, 156-159.
213. Recent examples of the use of this process include: a) M. Yamashita, K. Suzuki, Y. Kato, A. Iida, K. Ikai, P. M. Reddy, T. Oshikawa, J. Carbohydr. Chem. 1999, 18, 915-935; b) M. Moore, P. Norris, Tetrahedron Lett. 1998, 39, 7027-7030; c) D. J. Hlasta, J. H. Ackerman, J. Org. Chem. 1994, 59, 6184-6189; d) F. Palacios, A. M. Ochoa de Retana, J. Pagalday, Heterocyctes 1994, 38, 95-102; e) W. H. Pearson, S. C. Bergmeier, J. A. Chytra, Synthesis 1990, 156-159.
214. a) A. Marzinzik, A. V. Gontcharov, K. B. Sharpless, unpublished results;
215. b) R. Portmann (Novartis AG), WO-A 9802423, 1998 |Chem. Abstr. 1998, 128, 140707].
216. b) R. Portmann (Novartis AG), WO-A 9802423, 1998 |Chem. Abstr. 1998, 128, 140707].
217. a) T.-H. Chuang, K. B. Sharpless, Helv. Chim. Acta 2000, 83, 1734-1743;
218. b) J. Svete, A. Preseren, B. Stanovnik, L. Golic, S. Golic-Gradadolnik, J. Heterocycl. Chem. 1997, 34, 1323-1328.
219. a) P. Deslongchamps, Y. L. Dory, S. Li, Tetrahedron 2000, 56, 3533-3537, and references cited therein:
220. b) orally available drugs must be stable to the acidic environment of the stomach. For acetal and ketal examples, see: M. Jung, S. Lee, Bioorg. Med. Chem. Lett. 1998, 8, 1003-1006; for ketoconazole, itraconazole, and derivatives, see: J. Heeres, L. J. J. Backx, J. H. Mostmans, J. Van Cutsem, J. Med. Chem. 1979, 22, 1003-1005; T. Bergan, Antiinfect. Drugs Chemother. 1995, 13, 149-150; N. Sonino, F. Fallo, M. Boscaro, Med. Sci. Res. 1989, 17, 131-134; J. Bolos, S. Gubert, L. Anglada, A. Sacristan, J. A. Ortiz, J. Heterocycl. Chem. 1997, 34, 1709-1713; L.-F. Huang, J.-W. Kim, L. Bauer, G. Doss, J. Heterocycl. Chem. 1997, 34, 469-476.
221. b) orally available drugs must be stable to the acidic environment of the stomach. For acetal and ketal examples, see: M. Jung, S. Lee, Bioorg. Med. Chem. Lett. 1998, 8, 1003-1006; for ketoconazole, itraconazole, and derivatives, see: J. Heeres, L. J. J. Backx, J. H. Mostmans, J. Van Cutsem, J. Med. Chem. 1979, 22, 1003-1005; T. Bergan, Antiinfect. Drugs Chemother. 1995, 13, 149-150; N. Sonino, F. Fallo, M. Boscaro, Med. Sci. Res. 1989, 17, 131-134; J. Bolos, S. Gubert, L. Anglada, A. Sacristan, J. A. Ortiz, J. Heterocycl. Chem. 1997, 34, 1709-1713; L.-F. Huang, J.-W. Kim, L. Bauer, G. Doss, J. Heterocycl. Chem. 1997, 34, 469-476.
222. b) orally available drugs must be stable to the acidic environment of the stomach. For acetal and ketal examples, see: M. Jung, S. Lee, Bioorg. Med. Chem. Lett. 1998, 8, 1003-1006; for ketoconazole, itraconazole, and derivatives, see: J. Heeres, L. J. J. Backx, J. H. Mostmans, J. Van Cutsem, J. Med. Chem. 1979, 22, 1003-1005; T. Bergan, Antiinfect. Drugs Chemother. 1995, 13, 149-150; N. Sonino, F. Fallo, M. Boscaro, Med. Sci. Res. 1989, 17, 131-134; J. Bolos, S. Gubert, L. Anglada, A. Sacristan, J. A. Ortiz, J. Heterocycl. Chem. 1997, 34, 1709-1713; L.-F. Huang, J.-W. Kim, L. Bauer, G. Doss, J. Heterocycl. Chem. 1997, 34, 469-476.
223. b) orally available drugs must be stable to the acidic environment of the stomach. For acetal and ketal examples, see: M. Jung, S. Lee, Bioorg. Med. Chem. Lett. 1998, 8, 1003-1006; for ketoconazole, itraconazole, and derivatives, see: J. Heeres, L. J. J. Backx, J. H. Mostmans, J. Van Cutsem, J. Med. Chem. 1979, 22, 1003-1005; T. Bergan, Antiinfect. Drugs Chemother. 1995, 13, 149-150; N. Sonino, F. Fallo, M. Boscaro, Med. Sci. Res. 1989, 17, 131-134; J. Bolos, S. Gubert, L. Anglada, A. Sacristan, J. A. Ortiz, J. Heterocycl. Chem. 1997, 34, 1709-1713; L.-F. Huang, J.-W. Kim, L. Bauer, G. Doss, J. Heterocycl. Chem. 1997, 34, 469-476.
224. b) orally available drugs must be stable to the acidic environment of the stomach. For acetal and ketal examples, see: M. Jung, S. Lee, Bioorg. Med. Chem. Lett. 1998, 8, 1003-1006; for ketoconazole, itraconazole, and derivatives, see: J. Heeres, L. J. J. Backx, J. H. Mostmans, J. Van Cutsem, J. Med. Chem. 1979, 22, 1003-1005; T. Bergan, Antiinfect. Drugs Chemother. 1995, 13, 149-150; N. Sonino, F. Fallo, M. Boscaro, Med. Sci. Res. 1989, 17, 131-134; J. Bolos, S. Gubert, L. Anglada, A. Sacristan, J. A. Ortiz, J. Heterocycl. Chem. 1997, 34, 1709-1713; L.-F. Huang, J.-W. Kim, L. Bauer, G. Doss, J. Heterocycl. Chem. 1997, 34, 469-476.
225. b) orally available drugs must be stable to the acidic environment of the stomach. For acetal and ketal examples, see: M. Jung, S. Lee, Bioorg. Med. Chem. Lett. 1998, 8, 1003-1006; for ketoconazole, itraconazole, and derivatives, see: J. Heeres, L. J. J. Backx, J. H. Mostmans, J. Van Cutsem, J. Med. Chem. 1979, 22, 1003-1005; T. Bergan, Antiinfect. Drugs Chemother. 1995, 13, 149-150; N. Sonino, F. Fallo, M. Boscaro, Med. Sci. Res. 1989, 17, 131-134; J. Bolos, S. Gubert, L. Anglada, A. Sacristan, J. A. Ortiz, J. Heterocycl. Chem. 1997, 34, 1709-1713; L.-F. Huang, J.-W. Kim, L. Bauer, G. Doss, J. Heterocycl. Chem. 1997, 34, 469-476.
226. Z. Demko, D. Michel, B. Chao, K. B. Sharpless, unpublished results.
227. M. A. Winter, K. B. Sharpless, unpublished results.
228. E. Stevens, A. V. Gontcharov, K. B. Sharpless, unpublished results.
229. See ref. [40a] for 10- to 100-gram preparations of these crystalline aziridines.
230. T. Fukuyama, C.-K. Jow, M. Cheung. Tetrahedron Lett. 1995, 36, 6373-6374.
231. 63 candidates of Guida and co-workers in ref. [14] - that remain unexplored for the discovery of biologically active molecules.
232. a) A. E. Rubin, PhD thesis, The Scripps Research Institute (USA), 1999;
233. b) D. S. Nirschl, PhD thesis, The Scripps Research Institute (USA), 2000.