A New Generation of "Cholaphanes": Steroid-Derived Macrocyclic Hosts with Enhanced Solubility and Controlled Flexibility

Journal of Organic Chemistry

Volumn 62, Issue 24, 1997, Pages 8463-8473

  Bhattarai, Khadga M ^a   Davis, Anthony P ^a   Perry, Justin J ^a   Walter, Christopher J ^a   Menzer, Stephan ^b   Williams, David J ^b  

^a TRINITY COLLEGE DUBLIN   (Ireland)

^b IMPERIAL COLLEGE LONDON   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000714146     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo971272w     Document Type: Article

References (81)

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14. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
15. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
16. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
17. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
18. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
19. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
20. Recent examples: (a) Davis, A. P.; Walsh, J. J. J. Chem. Soc., Chem. Commun. 1996, 449. (b) Davis, A. P.; Menzer, S.; Walsh, J. J.; Williams, D. J. J. Chem. Soc., Chem. Commun. 1996, 453. (c) Davis, A. P.; Gilmer, J. F.; Perry, J. J. Angew. Chem., Int. Ed. Engl. 1996, 35, 1312. (d) Kolehmainen, E.; Tamminen, J.; Lappalainen, K.; Torkkel, T.; Seppala, R. Synthesis 1996, 1082. (e) Irie, S.; Yamamoto, M.; Kishikawa, K.; Kohmoto, S.; Yamada, K. Synthesis 1996, 1135. (f) Kohmoto, S.; Fukui, D.; Nagashima, T.; Kishikawa, K.; Yamamoto, M.; Yamada, K. J. Chem. Soc., Chem. Commun. 1996, 1869. (g) Bonar-Law, R. P. J. Am. Chem. Soc. 1995, 117, 12397. (h) Bonar-Law, R. P.; Sanders, J. K. M. J. Am. Chem. Soc. 1995, 117, 259. (i) Albert, D.; Feigl, M. Tetrahedron Lett. 1994, 35, 565.
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31. For recent illustrations of this principle, featuring inverse correlations between flexibility and enantioselectivity, see: (a) Yoon, S. S.; Georgiadis, T. M.; Still, W. C. Tetrahedron Lett. 1993, 34, 6697. (b) Cuntze, J.; Owens, L.; Alcazar, V.; Seiler, P.; Diederich, F. Helv. Chim. Acta 1995, 78, 367.
32. For recent illustrations of this principle, featuring inverse correlations between flexibility and enantioselectivity, see: (a) Yoon, S. S.; Georgiadis, T. M.; Still, W. C. Tetrahedron Lett. 1993, 34, 6697. (b) Cuntze, J.; Owens, L.; Alcazar, V.; Seiler, P.; Diederich, F. Helv. Chim. Acta 1995, 78, 367.
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39. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
40. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
41. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
42. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
43. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
44. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
45. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
46. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
47. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
48. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
49. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
50. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
51. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
52. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
53. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
54. For other studies on carbohydrate recognition, see e.g. refs 3b, 3f, 3h, 7b, and: (a) Aoyama, Y.; Tanaka, Y.; Sugahara, S. J. Am. Chem. Soc. 1989, 111, 5397. (b) Kikuchi, Y.; Tanaka, Y.; Sutaro, S.; Kobayashi, K.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc. 1992, 114, 10302. (c) Liu, R.; Still, W. C. Tetrahedron Lett. 1993, 34, 2573. (d) Savage, P. B.; Gellman, S. H. J. Am. Chem. Soc. 1993, 115, 10448. (e) Das, G.; Hamilton, A. D. J. Am. Chem. Soc. 1994, 116, 11139. (f) Huang, C.-Y.; Cabell, L. A.; Anslyn, E. V. J. Am. Chem. Soc. 1994, 116, 2778. (g) Coterón, J. M.; Vicent, C.; Bosso, C.; Penadés, S. J. Am. Chem. Soc. 1993, 115, 10066. (h) Eliseev, A. V.; Schneider, H.-J. J. Am. Chem. Soc. 1994, 116, 6081. (i) Mohler, L. K.; Czarnik, A. W. J. Am. Chem. Soc. 1993, 115, 2998. (j) Morin, G. T.; Hughes, M. P.; Paugam, M.-F.; Smith, B. D. J. Am. Chem. Soc. 1994, 116, 8895. (k) Deng, G.; James, T. D.; Shinkai, S. J. Am. Chem. Soc. 1994, 116, 4567. (l) James, T. D.; Sandanayake, K. R. A. S.; Shinkai, S. Angew. Chem., Int. Ed. Engl. 1996, 35, 1911. (m) Mizutani, T.; Murakami, T.; Matsumi, N.; Kurahashi, T.; Ogoshi, H. J. Chem. Soc., Chem. Commun. 1995, 1257. (n) Anderson, S.; Neidlein, U.; Gramlich, V.; Diederich, F. Angew. Chem., Int. Ed. Engl. 1995, 34, 1596. (o) Neidlein, U.; Diederich, F. J. Chem. Soc., Chem. Commun. 1996, 1493. (p) Inouye, M.; Miyake, T.; Furusyo, M.; Nakazumi, H. J. Am. Chem. Soc. 1995, 117, 12416.
55. Davis, A. P.; Egan, T. J.; Orchard, M. G.; Cunningham, D.; McArdle, P. Tetrahedron 1992, 48, 8725.
56. Davis, A. P.; Orchard, M. G. J. Chem. Soc., Perkin Trans. 1 1993, 919.
57. cf. refs 3a - c.
58. Schteingart, C. D.; Hofmann, A. F. J. Lipid Res. 1988, 29, 1387.
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61. (a) Davis, A. P.; Bhattarai, K. M. Tetrahedron 1995, 51, 8033.
62. See also: (b) Liao, Y.; Huang, Y.-Z. Tetrahedron Lett. 1990, 31, 5897. (c) Chen, C.; Huang, Y.-Z.; Shen, Y.; Liao, Y. Heteroatom Chem. 1990, 1,49.
63. See also: (b) Liao, Y.; Huang, Y.-Z. Tetrahedron Lett. 1990, 31, 5897. (c) Chen, C.; Huang, Y.-Z.; Shen, Y.; Liao, Y. Heteroatom Chem. 1990, 1,49.
64. Most common N-protecting groups contain acidic protons or polarized multiple bonds which will quench a Grignard reagent, Obvious exceptions, such as silyl groups, do not eliminate N-basicity, which can interfere with the reactivity of a derived cuprate. For further discussion see ref 11.
65. Davis, A. P.; Egan, T. J. Tetrahedron Lett. 1992, 33, 8125.
66. Carlson, G. L.; Belobaba, D. T. E.; Hofmann, A. F.; Wedmid, Y. Steroids 1977, 30, 787.
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68. Lindgren, B. O.; Nilsson, T. Acta Chem. Scand. 1973, 27, 888.
69. Davis, A. P.; Walsh, J. J. Tetrahedron Lett. 1994, 35, 4865.
70. Details to be published separately.
71. There are 15 O-H···O hydrogen bonds which range in distance from 2.73 to 3.05 Å, and one N-H···O hydrogen bond (3.07 Å) from one of the amide nitrogen atoms to one of the included water molecules.
72. 4, as a 2:1 host:guest complex, see ref 9b.
73. Still, W. C.; Kahn, M.; Mitra, A. J. Org. Chem. 1978, 43, 2923.
74. Perrin, D. D.; Armanego, W. F.; Perrin, D. R. Purification of Laboratory Chemicals; 2nd ed.; Pergamon: Oxford, 1980.
75. Cleavage of the tert-butyl ether unit by TFA yields a trifluoroacetate which must then be hydrolyzed under basic conditions. The trifluoroacetate is not readily distinguished by TLC from the starting ether, necessitating hydrolysis of reaction samples as well as the bulk product.
76. f values.
77. CAUTION: when used in chlorinated solvents, this reagent can lead to explosive side-products. Workers intending to repeat this preparation should seek an alternative to dichloromethane as solvent. See ref 11 and: Li, C.; Shih, T.-L.; Jeong, J. U.; Arasappan, A.; Fuchs, P. L. Tetrahedron Lett. 1994, 35, 2645.
78. In line with previous experience (refs 8d, 11) analytical samples of cholaphanes 3 and 4 appeared to be solvated. In all cases the data was consistent with integral numbers of water molecules, possibly acquired from atmospheric exposure after drying.
79. A minor slower-running impurity proved to be 3β-[bis(butoxycarbonyl)methyl]-3α-[p-(tert-butoxymethyl)phenyl]- 7α-formyloxy-12α-hydroxy-24-nor-5β-cholan-22(23)-ene, presumably arising from deformylation of 19. In large-scale work this was reformylated and carried through to 20.
80. Deranleau, D. A. J. Am. Chem. Soc. 1969, 91, 4044. Connors, K. A. Binding Constants; Wiley: New York, 1987; p 66.
81. Deranleau, D. A. J. Am. Chem. Soc. 1969, 91, 4044. Connors, K. A. Binding Constants; Wiley: New York, 1987; p 66.