Two-Dimensional NMR Analysis of Acetonide Derivatives in the Assignment of Polyol Chains: The Absolute Configurations of Dermostatins A and B

Journal of Organic Chemistry

Volumn 62, Issue 9, 1997, Pages 2925-2934

  Rychnovsky, Scott D ^a   Richardson, Timothy I ^a   Rogers, Bruce N ^a  

^a NONE

Author keywords

[No Author keywords available]

Indexed keywords

DERMOSTATIN A; DERMOSTATIN B; POLYOL;

ARTICLE; DRUG STRUCTURE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOCHEMISTRY;

EID: 0031007512     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo970213f     Document Type: Article

References (83)

1. The structure of amphotericin B was determined by X-ray analysis of its N-iodoacetyl derivative: (a) Mechlinski, W.; Schaffner, C. P.; Ganis, P.; Avitabile, G. Tetrahedron Lett. 1970, 3873-6. (b) Ganis, P.; Avitabile, G.; Mechlinski, W.; Schaffner, C. P. J. Am. Chem. Soc. 1971, 93, 4560-4. The structure of roxaticin was determined by X-ray analysis of its heptaacetate derivative: (c) Maehr, H.; Yang, R.; Hong, L. N.; Liu, C. M.; Hatada, M. H.; Todaro, L. J. J. Org. Chem. 1989, 54, 3816-3819.
2. The structure of amphotericin B was determined by X-ray analysis of its N-iodoacetyl derivative: (a) Mechlinski, W.; Schaffner, C. P.; Ganis, P.; Avitabile, G. Tetrahedron Lett. 1970, 3873-6. (b) Ganis, P.; Avitabile, G.; Mechlinski, W.; Schaffner, C. P. J. Am. Chem. Soc. 1971, 93, 4560-4. The structure of roxaticin was determined by X-ray analysis of its heptaacetate derivative: (c) Maehr, H.; Yang, R.; Hong, L. N.; Liu, C. M.; Hatada, M. H.; Todaro, L. J. J. Org. Chem. 1989, 54, 3816-3819.
3. The structure of amphotericin B was determined by X-ray analysis of its N-iodoacetyl derivative: (a) Mechlinski, W.; Schaffner, C. P.; Ganis, P.; Avitabile, G. Tetrahedron Lett. 1970, 3873-6. (b) Ganis, P.; Avitabile, G.; Mechlinski, W.; Schaffner, C. P. J. Am. Chem. Soc. 1971, 93, 4560-4. The structure of roxaticin was determined by X-ray analysis of its heptaacetate derivative: (c) Maehr, H.; Yang, R.; Hong, L. N.; Liu, C. M.; Hatada, M. H.; Todaro, L. J. J. Org. Chem. 1989, 54, 3816-3819.
4. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
5. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
6. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
7. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
8. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
9. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
10. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
11. Nystatin: (a) Prandi, J.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4517-20. (b) Lancelin, J.-M.; Beau, J.-M. Tetrahedron Lett. 1989, 30, 4521-4. (c) See also: Nicolaou, K. C.; Ahn, K. H. Tetrahedron Lett. 1989, 30, 1217-20. Vacidin A: (d) Sowinski, P.; Gariboldi, P.; Czerwinski, A.; Borowski, E. J. Antibiot. 1989, 42, 1631-8. (e) Sowinski, P.; Gariboldi, P.; Pawlak, J. K.; Borowski, E. J. Antibiot. 1989, 42, 1639-42. Pimaricin: (f) Lancelin, J.-M.; Beau, J.-M. J. Am. Chem. Soc. 1990, 112, 4060-1. (g) Lancelin, J.-M.; Beau, J.-M. Bull. Soc. Chim. Fr. 1995, 132, 215-23. Candidin: (h) Pawlak, J.; Sowinski, P.; Borowski, E.; Gariboldi, P. J. Antibiot. 1993, 46, 1598-1603.
12. Pentamycin: (a) Oishi T. Pure Appl. Chem. 1989, 67, 427-30. (b) Nakata, T.; Hata, N.; Suenaga, T.; Oishi, T. Abstract of Papers, 30th Symposium on the Chemistry of Natural Products, Fukuoka, Oct 1988, p 540.
13. Pentamycin: (a) Oishi T. Pure Appl. Chem. 1989, 67, 427-30. (b) Nakata, T.; Hata, N.; Suenaga, T.; Oishi, T. Abstract of Papers, 30th Symposium on the Chemistry of Natural Products, Fukuoka, Oct 1988, p 540.
14. Mycoticins A and B: (a) Schreiber, S. L.; Goulet, M. T. Tetrahedron Lett. 1987, 28, 6001-4. (b) Schreiber, S. L.; Goulet, M. T.; Sammakia, T. Tetrahedron Lett. 1987, 28, 6005-8. (c) Schreiber, S. L.; Goulet, M. T. J. Am. Chem. Soc. 1987, 109, 8120-2. (d) Goulet, M. Ph.D. Thesis, Yale University, 1988.
15. Mycoticins A and B: (a) Schreiber, S. L.; Goulet, M. T. Tetrahedron Lett. 1987, 28, 6001-4. (b) Schreiber, S. L.; Goulet, M. T.; Sammakia, T. Tetrahedron Lett. 1987, 28, 6005-8. (c) Schreiber, S. L.; Goulet, M. T. J. Am. Chem. Soc. 1987, 109, 8120-2. (d) Goulet, M. Ph.D. Thesis, Yale University, 1988.
16. Mycoticins A and B: (a) Schreiber, S. L.; Goulet, M. T. Tetrahedron Lett. 1987, 28, 6001-4. (b) Schreiber, S. L.; Goulet, M. T.; Sammakia, T. Tetrahedron Lett. 1987, 28, 6005-8. (c) Schreiber, S. L.; Goulet, M. T. J. Am. Chem. Soc. 1987, 109, 8120-2. (d) Goulet, M. Ph.D. Thesis, Yale University, 1988.
17. Mycoticins A and B: (a) Schreiber, S. L.; Goulet, M. T. Tetrahedron Lett. 1987, 28, 6001-4. (b) Schreiber, S. L.; Goulet, M. T.; Sammakia, T. Tetrahedron Lett. 1987, 28, 6005-8. (c) Schreiber, S. L.; Goulet, M. T. J. Am. Chem. Soc. 1987, 109, 8120-2. (d) Goulet, M. Ph.D. Thesis, Yale University, 1988.
18. Roflamycoin: (a) Rychnovsky, S. D.; Griesgraber, G.; Schlegel, R. J. Am. Chem. Soc. 1994, 116, 2623-4. (b) Rychnovsky, S. D.; Griesgraber, G.; Schlegel, R. J. Am. Chem. Soc. 1995, 117, 197-210.
19. Roflamycoin: (a) Rychnovsky, S. D.; Griesgraber, G.; Schlegel, R. J. Am. Chem. Soc. 1994, 116, 2623-4. (b) Rychnovsky, S. D.; Griesgraber, G.; Schlegel, R. J. Am. Chem. Soc. 1995, 117, 197-210.
20. Filipin III: (a) Rychnovsky, S. D.; Richardson, T. I. Angew. Chem., Int. Ed. Engl. 1995, 34, 1227-30. (b) Richardson, T. I.; Rychnovsky, S. D. J. Org. Chem. 1996, 61, 4219-31.
21. Filipin III: (a) Rychnovsky, S. D.; Richardson, T. I. Angew. Chem., Int. Ed. Engl. 1995, 34, 1227-30. (b) Richardson, T. I.; Rychnovsky, S. D. J. Org. Chem. 1996, 61, 4219-31.
22. For reviews, see: (a) Rychnovsky, S. D. Chem. Rev. 1995, 95, 2021-40. (b) Beau, J. M. In Recent Progress in the Chemistry of Synthetic Antibiotics; Lukacs, G., Ohno, M., Eds.; Springer: Berlin, 1990; pp 135-182. (c) Omura, S.; Tanaka, H. In Macrolide Antibiotics: Chemistry, Biology, and Practice; Omura, S., Ed.; Academic Press: New York, 1984; pp 351-404.
23. For reviews, see: (a) Rychnovsky, S. D. Chem. Rev. 1995, 95, 2021-40. (b) Beau, J. M. In Recent Progress in the Chemistry of Synthetic Antibiotics; Lukacs, G., Ohno, M., Eds.; Springer: Berlin, 1990; pp 135-182. (c) Omura, S.; Tanaka, H. In Macrolide Antibiotics: Chemistry, Biology, and Practice; Omura, S., Ed.; Academic Press: New York, 1984; pp 351-404.
24. For reviews, see: (a) Rychnovsky, S. D. Chem. Rev. 1995, 95, 2021-40. (b) Beau, J. M. In Recent Progress in the Chemistry of Synthetic Antibiotics; Lukacs, G., Ohno, M., Eds.; Springer: Berlin, 1990; pp 135-182. (c) Omura, S.; Tanaka, H. In Macrolide Antibiotics: Chemistry, Biology, and Practice; Omura, S., Ed.; Academic Press: New York, 1984; pp 351-404.
25. Circular dichroism (CD) methods have been developed by both Mori and Nakanishi to assign the absolute configuration of 1,3-skipped polyols. (a) Mori, Y.; Kohchi, Y.; Suzuki, M.; Furukawa, H. J. Am. Chem. Soc. 1992, 114, 3557-9. (b) Mori, Y.; Sawada, T.; Sasaki, N.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 1651-6 and references cited therein. (c) Zhou, P.; Zhao, N.; Rele, D. N.; Berova, N.; Nakanishi, N. J. Am. Chem. Soc. 1993, 115, 9313-14. (d) Zhao, N.; Zhou, P.; Berova, N.; Nakanishi, K. Chirality 1995, 7, 636-51. These CD methods are appropriate for determining the absolute configuration of a few centers at the end of a polyol chain, but are not well suited for configurational assignments in the middle of a polyol chain, and to date they have not played a major role in the stereochemical assignment of a polyene macrolide antibiotic. The simple dibenzoate CD method has been used to determine the absolute configuration of a single relationship in a polyol derivative: Pawlak, J.; Nakanishi, K.; Iwashita, T.; Borowski, E. J. Org. Chem. 1987, 52, 2896-901.
26. Circular dichroism (CD) methods have been developed by both Mori and Nakanishi to assign the absolute configuration of 1,3-skipped polyols. (a) Mori, Y.; Kohchi, Y.; Suzuki, M.; Furukawa, H. J. Am. Chem. Soc. 1992, 114, 3557-9. (b) Mori, Y.; Sawada, T.; Sasaki, N.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 1651-6 and references cited therein. (c) Zhou, P.; Zhao, N.; Rele, D. N.; Berova, N.; Nakanishi, N. J. Am. Chem. Soc. 1993, 115, 9313-14. (d) Zhao, N.; Zhou, P.; Berova, N.; Nakanishi, K. Chirality 1995, 7, 636-51. These CD methods are appropriate for determining the absolute configuration of a few centers at the end of a polyol chain, but are not well suited for configurational assignments in the middle of a polyol chain, and to date they have not played a major role in the stereochemical assignment of a polyene macrolide antibiotic. The simple dibenzoate CD method has been used to determine the absolute configuration of a single relationship in a polyol derivative: Pawlak, J.; Nakanishi, K.; Iwashita, T.; Borowski, E. J. Org. Chem. 1987, 52, 2896-901.
27. Circular dichroism (CD) methods have been developed by both Mori and Nakanishi to assign the absolute configuration of 1,3-skipped polyols. (a) Mori, Y.; Kohchi, Y.; Suzuki, M.; Furukawa, H. J. Am. Chem. Soc. 1992, 114, 3557-9. (b) Mori, Y.; Sawada, T.; Sasaki, N.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 1651-6 and references cited therein. (c) Zhou, P.; Zhao, N.; Rele, D. N.; Berova, N.; Nakanishi, N. J. Am. Chem. Soc. 1993, 115, 9313-14. (d) Zhao, N.; Zhou, P.; Berova, N.; Nakanishi, K. Chirality 1995, 7, 636-51. These CD methods are appropriate for determining the absolute configuration of a few centers at the end of a polyol chain, but are not well suited for configurational assignments in the middle of a polyol chain, and to date they have not played a major role in the stereochemical assignment of a polyene macrolide antibiotic. The simple dibenzoate CD method has been used to determine the absolute configuration of a single relationship in a polyol derivative: Pawlak, J.; Nakanishi, K.; Iwashita, T.; Borowski, E. J. Org. Chem. 1987, 52, 2896-901.
28. Circular dichroism (CD) methods have been developed by both Mori and Nakanishi to assign the absolute configuration of 1,3-skipped polyols. (a) Mori, Y.; Kohchi, Y.; Suzuki, M.; Furukawa, H. J. Am. Chem. Soc. 1992, 114, 3557-9. (b) Mori, Y.; Sawada, T.; Sasaki, N.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 1651-6 and references cited therein. (c) Zhou, P.; Zhao, N.; Rele, D. N.; Berova, N.; Nakanishi, N. J. Am. Chem. Soc. 1993, 115, 9313-14. (d) Zhao, N.; Zhou, P.; Berova, N.; Nakanishi, K. Chirality 1995, 7, 636-51. These CD methods are appropriate for determining the absolute configuration of a few centers at the end of a polyol chain, but are not well suited for configurational assignments in the middle of a polyol chain, and to date they have not played a major role in the stereochemical assignment of a polyene macrolide antibiotic. The simple dibenzoate CD method has been used to determine the absolute configuration of a single relationship in a polyol derivative: Pawlak, J.; Nakanishi, K.; Iwashita, T.; Borowski, E. J. Org. Chem. 1987, 52, 2896-901.
29. Circular dichroism (CD) methods have been developed by both Mori and Nakanishi to assign the absolute configuration of 1,3-skipped polyols. (a) Mori, Y.; Kohchi, Y.; Suzuki, M.; Furukawa, H. J. Am. Chem. Soc. 1992, 114, 3557-9. (b) Mori, Y.; Sawada, T.; Sasaki, N.; Furukawa, H. J. Am. Chem. Soc. 1996, 118, 1651-6 and references cited therein. (c) Zhou, P.; Zhao, N.; Rele, D. N.; Berova, N.; Nakanishi, N. J. Am. Chem. Soc. 1993, 115, 9313-14. (d) Zhao, N.; Zhou, P.; Berova, N.; Nakanishi, K. Chirality 1995, 7, 636-51. These CD methods are appropriate for determining the absolute configuration of a few centers at the end of a polyol chain, but are not well suited for configurational assignments in the middle of a polyol chain, and to date they have not played a major role in the stereochemical assignment of a polyene macrolide antibiotic. The simple dibenzoate CD method has been used to determine the absolute configuration of a single relationship in a polyol derivative: Pawlak, J.; Nakanishi, K.; Iwashita, T.; Borowski, E. J. Org. Chem. 1987, 52, 2896-901.
30. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
31. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
32. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
33. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
34. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
35. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
36. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
37. Dermostatin is an oxopolyene macrolide antibiotic that was isolated from the mycelium of Streptomyces viridogriseus Thirum. (a) Thirumalachar, M. J.; Menon, S. K. Hind. Antibiot. Bull. 1962, 4, 106-8. (b) Bhate, D. S.; Ambekar, G. R.; Bhatnagar, K. K. Hind. Antibiot. Bull. 1962, 4, 159-162. It consists of two components, dermostatins A and B, whose flat structure have been determined, (a) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S.; Swami, M. B. J. Antibiot. 1973, 26, 475-7. (b) Narasimhachari, N.; Swami, M. B. Chemotherapy 1968, 13, 181-7. (c) Narasimhachari, N.; Swami, M. B. J. Antibiot. 1970, 23, 566. (d) Pandey, R. C.; Rinehart, K. L., Jr.; Millington, D. S. Hind. Antibiot. Bull. 1980, 22, 47-61. (e) Swamy, M. B.; Sastry, M. K.; Nanda, R. K. Hind. Antibiot. Bull. 1994, 36, 6-20. Dermostatin shows antifungal activity comparable to that of amphotericin B against a large number of human pathogens including dermatomycosis. Gordee, R. S.; Butler, T. F.; Narasimhachari, N. J. Antibiot. 1971, 24, 561-5.
38. (a) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett. 1990, 31, 945-8. (b) Evans, D. A.; Rieger, D. L.; Gage, J. R. Tetrahedron Lett. 1990, 31, 7099-7102. (c) Rychnovsky, S. D.; Rogers, B.; Yang, G. J. Org. Chem. 1993, 58, 3511-15.
39. (a) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett. 1990, 31, 945-8. (b) Evans, D. A.; Rieger, D. L.; Gage, J. R. Tetrahedron Lett. 1990, 31, 7099-7102. (c) Rychnovsky, S. D.; Rogers, B.; Yang, G. J. Org. Chem. 1993, 58, 3511-15.
40. (a) Rychnovsky, S. D.; Skalitzky, D. J. Tetrahedron Lett. 1990, 31, 945-8. (b) Evans, D. A.; Rieger, D. L.; Gage, J. R. Tetrahedron Lett. 1990, 31, 7099-7102. (c) Rychnovsky, S. D.; Rogers, B.; Yang, G. J. Org. Chem. 1993, 58, 3511-15.
41. Rychnovsky, S. D.; Skalitzky, D. J.; Pathirana, C.; Jensen, P. R.; Fenical, W. J. Am. Chem. Soc. 1992, 114, 671-677.
42. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
43. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
44. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
45. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
46. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
47. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
48. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
49. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
50. 13C acetonide analysis used for structure determination, see: (a) Hoye, T. R.; Jimenez, J. I.; Shier, W. T. J. Am. Chem. Soc. 1994, 116, 9409-9410. (b) Harmange, J.-C.; Boyle, C. D.; Kishi, Y. Tetrahedron Lett. 1994, 35, 6819-6822. (c) Golakoti, T.; Ohtani, I.; Patterson, G. M. L.; Moore, R. E.; Corbett, T. H.; Valeriote, F. A.; Demchik, L. J. Am. Chem. Soc. 1994, 116, 4729-4737. (d) Mori, Y.; Kawajiri, N.; Furukawa, H.; Moore, R. E. Tetrahedron 1994, 50, 11133-11142. (e) Seki-Asano, M.; Tsuchida, Y.; Hanada, K.; Mizoue, K. J. Antibiot. 1994, 47, 1234-1241. (f) Murata, H.; Ohama, I.; Harada, K.-I.; Suzuki, M.; Ikemoto, T.; Shibuya, T.; Haneishi, T.; Torikata, A.; Itezono, Y.; Nakayama, N. J. Antibiot. 1995, 48, 850-62. (g) Golakoti, T.; Ohtani, I.; Heltzel, C. E.; Husebo, T. L.; Jensen, C. M.; Larson, L. K.; Patterson, G. M. L.; Moore, R. E.; Mooberry, S. L.; Corbett, T. H.; Valeriote, F. A. J. Am. Chem. Soc. 1995, 117, 12030-12049. (h) Searl, P. A.; Richter, R. K.; Molinski, T. F. J. Org. Chem. 1996, 61, 4073-4079. (i) Suenaga, K.; Mutou, T.; Shibata, T.; Itoh, T.; Kigoshi, H.; Yamada, K. Tetrahedron Lett. 1996, 37, 6771-6774.
51. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
52. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
53. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
54. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
55. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
56. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
57. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
58. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
59. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
60. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
61. 13C method has been cited in the literature over 100 times. For recent examples, see: (a) Yokokawa, F.; Hamada, Y.; Shiori, T. Chem. Commun. 1996, 871-872. (b) Kim, K. S.; Park, H. B.; Kim, J. Y.; Ahn, Y. H.; Jeong, I. H. Tetrahedron Lett. 1996, 37, 1249-1252. (c) Paterson, I.; Perkins, M. V. Tetrahedron 1996, 52, 1811-1834. (d) Travares, F.; Lawson, J. P.; Meyery, A. I. J. Am. Chem. Soc. 1996, 218, 3303-3304. (e) Szymoniak, J.; Lefranc, H.; Moise, C. J. Org. Chem. 1996, 61, 3926-3928. (f) Hatakeyama, S.; Fukuyama, H.; Mukugi, Y.; Irie, H. Tetrahedron Lett. 1996, 37, 4047-4050. (g) Achmatowicz, B.; Jankowski, P.; Wicha, J. Tetrahedron Lett. 1996, 37, 5589-5592. (h) Scarlato, G. R.; DeMattei, J. A.; Chong, L. S.; Ogawa, A. K.; Lin, M. R.; Armstrong, R. W. J. Org. Chem. 1996, 61, 6139-6152. (i) Nagasawa, K.; Shimizu, I.; Nakata, T. Tetrahedron Lett. 1996, 37, 6881-6884. (j) Hamada, Y.; Yokokawa, F.; Kabeya, M.; Hatano, K.; Kurono, Y.; Shioiri, T. Tetrahedron 1996, 52, 8297-8306. (k) Nacro, K.; Baltas, M.; Escudier, J.-M.; Gorrichon Tetrahedron 1996, 52, 9047-9056.
62. 13C acetonide strategy during the structure determination of filipin III. At that time we had already completed the structure determination of filipin III (ref 6) but later reanalyzed several of the complex polyacetonides from that project and demonstrated that the new integrated strategy was successful. This work has been described in a number of seminars beginning with one on December 4, 1995, at U.C. San Diego but has not before appeared in print. The stereochemical assignment of dermostatin A was recently presented: Rychnovsky, S. D.; Richardson, T. I. Abstract of Papers, 212th National Meeting of the American Chemical Society, Orlando, FL; American Chemical Society: Washington, DC, 1996; ORG 436.
63. Examples of 2D NMR analysis of acetonides: (1) Ojika, M.; Nagoya, T.; Yamada, K. Tetrahedron Lett. 1995, 36, 7491-7494. Lindel, T.; Jensen, P. R.; Fenical, W. Tetrahedron Lett. 1996, 37, 1327-1330.
64. Examples of 2D NMR analysis of acetonides: (1) Ojika, M.; Nagoya, T.; Yamada, K. Tetrahedron Lett. 1995, 36, 7491-7494. Lindel, T.; Jensen, P. R.; Fenical, W. Tetrahedron Lett. 1996, 37, 1327-1330.
65. Piatini, U.; Sorenson, O. W.; Ernst, R. R. J. Am. Chem. Soc. 1982, 104, 6800-1.
66. (a) Bax, A.; Davis, D. G. J. Magn. Reson. 1985, 63, 207.
67. (b) Bax, A. J. Magn. Reson. 1988, 77, 134.
68. Bax, A.; Ikura, M.; Kay, L. E.; Torchia, D. A.; Tschudin, R. J. Magn. Reson. 1990, 86, 304.
69. Full spectral data for compounds 4-7, including peak assignments and 2D NMR data, can be found in the Experimental Section or the Supporting Information.
70. Ohtani, T.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092-6.
71. Proton NMR analysis of a combined sample of 11 showed no peak doubling.
72. For CD spectra, see Supporting Information.
73. See the Supporting Information for comparative NMR's of the Mosher esters 15 and 17.
74. Gage, J. R.; Evans, D. A. Org. Synth. 1989, 68, 83-90 and references cited therein.
75. 2-acetone (#29,918-9) at $438 for 1 g.
76. Possible applications of this exciting new tool would be in the configurational assignments of polyol natural products such as aflastatin A, linearmycin, or RK-397. (a) Sakuda, S.; Ono, M.; Furihata, K.; Nakayama, J.; Suzuki, A.; Isogai, A. J. Am. Chem. Soc. 1996, 118, 7855-7856. (b) Sakuda, S.; Gucebigol, U.; Itoh, M.; Nishimura, T.; Yamada, Y. Tetrahedron Lett. 1995, 36, 2777-80. (c) Koshino, H.; Kobinata, K.; Isono, K.; Osada, H. J. Antibiot. 1993, 46, 1619-21.
77. Possible applications of this exciting new tool would be in the configurational assignments of polyol natural products such as aflastatin A, linearmycin, or RK-397. (a) Sakuda, S.; Ono, M.; Furihata, K.; Nakayama, J.; Suzuki, A.; Isogai, A. J. Am. Chem. Soc. 1996, 118, 7855-7856. (b) Sakuda, S.; Gucebigol, U.; Itoh, M.; Nishimura, T.; Yamada, Y. Tetrahedron Lett. 1995, 36, 2777-80. (c) Koshino, H.; Kobinata, K.; Isono, K.; Osada, H. J. Antibiot. 1993, 46, 1619-21.
78. Possible applications of this exciting new tool would be in the configurational assignments of polyol natural products such as aflastatin A, linearmycin, or RK-397. (a) Sakuda, S.; Ono, M.; Furihata, K.; Nakayama, J.; Suzuki, A.; Isogai, A. J. Am. Chem. Soc. 1996, 118, 7855-7856. (b) Sakuda, S.; Gucebigol, U.; Itoh, M.; Nishimura, T.; Yamada, Y. Tetrahedron Lett. 1995, 36, 2777-80. (c) Koshino, H.; Kobinata, K.; Isono, K.; Osada, H. J. Antibiot. 1993, 46, 1619-21.
79. For a general experimental section and NMR parameters, see Supporting Information.
80. Column used was a 21.4 mm × 25 cm Rainin Microsorb C18 reversed phase Dynamax column.
81. (a) Pandey, R. C. U.S. Patent 5,210,226, 1993.
82. (b) Pandey, R. C. U.S. Patent 5,159,002, 1992.
83. When the nonaacetates from dermostatins A and B were combined and analyzed by HPLC, a single peak was observed.