Synthesis and absolute stereochemical assignment of (+)-miyakolide

Journal of the American Chemical Society

Volumn 121, Issue 29, 1999, Pages 6816-6826

  Evans, David A ^a   Ripin, David H B ^a   Halstead, David P ^a   Campos, Kevin R ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

MACROLIDE; MIYAKOLIDE; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; COMPLEX FORMATION; CONFORMATION; ESTERIFICATION; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033612754     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja990789h     Document Type: Article

References (111)

1. (a) Seebach, D. Angew. Chem., Int. Ed. Engl. 1990, 29, 1320-1367.
2. (b) Ireland, R. E. Aldrichim. Acta 1988, 21, 59-69.
3. (c) Norcross, R. D.; Paterson, I. Chem. Rev. 1995, 95, 2041-2114.
4. Synthesis has been used as a tool to produce isotopically labeled putative biosynthetic intermediates that are fed to the producing plant or animal in order to study their incorporation into the biosynthetic pathway. Some recent examples in the field of polyketide biosynthesis include: (a) Cane, D. E.; Luo, G. J. Am. Chem. Soc. 1995, 117, 6633-6634. (b) Yue, S.; Duncan, J. S.; Yamamoto, Y.; Hutchinson, C. R. J. Am. Chem. Soc. 1987, 109, 1253-1254.
5. Synthesis has been used as a tool to produce isotopically labeled putative biosynthetic intermediates that are fed to the producing plant or animal in order to study their incorporation into the biosynthetic pathway. Some recent examples in the field of polyketide biosynthesis include: (a) Cane, D. E.; Luo, G. J. Am. Chem. Soc. 1995, 117, 6633-6634. (b) Yue, S.; Duncan, J. S.; Yamamoto, Y.; Hutchinson, C. R. J. Am. Chem. Soc. 1987, 109, 1253-1254.
6. Proposed biosynthetic transformations have been reproduced in laboratory syntheses of natural products in order to test their practicality outside of the biological system and take advantage of the powerful transformations. Some examples include: (a) Johnson, W. S.; Gravestock, M. B.; McCarry, B. E. J. Am. Chem. Soc. 1971, 93, 4332-4334. (b) Gravestock, M. B.; Johnson, W. S.; McCarry, B. E.; Parry, R. J.; Ratcliffe, B, E. J. Am. Chem. Soc. 1978, 100, 4274-4282. (c) Chapman, O. L.; Engel, M. R.; Springer, J. P.; Clardy, J. C. J. Am. Chem. Soc. 1971, 93, 6696- 6698. (d) Nicolaou, K. C.; Petasis, N. A.; Zipkin, R. E. J. Am. Chem. Soc. 1982, 104, 5560-5562. (e) Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem. Soc. 1995, 117, 3448-3467. (f) Williams, D. R.; Coleman, P. J.; Henry, S. S. J. Am. Chem. Soc. 1993, 115, 11654-11655.
7. Proposed biosynthetic transformations have been reproduced in laboratory syntheses of natural products in order to test their practicality outside of the biological system and take advantage of the powerful transformations. Some examples include: (a) Johnson, W. S.; Gravestock, M. B.; McCarry, B. E. J. Am. Chem. Soc. 1971, 93, 4332-4334. (b) Gravestock, M. B.; Johnson, W. S.; McCarry, B. E.; Parry, R. J.; Ratcliffe, B, E. J. Am. Chem. Soc. 1978, 100, 4274-4282. (c) Chapman, O. L.; Engel, M. R.; Springer, J. P.; Clardy, J. C. J. Am. Chem. Soc. 1971, 93, 6696- 6698. (d) Nicolaou, K. C.; Petasis, N. A.; Zipkin, R. E. J. Am. Chem. Soc. 1982, 104, 5560-5562. (e) Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem. Soc. 1995, 117, 3448-3467. (f) Williams, D. R.; Coleman, P. J.; Henry, S. S. J. Am. Chem. Soc. 1993, 115, 11654-11655.
8. Proposed biosynthetic transformations have been reproduced in laboratory syntheses of natural products in order to test their practicality outside of the biological system and take advantage of the powerful transformations. Some examples include: (a) Johnson, W. S.; Gravestock, M. B.; McCarry, B. E. J. Am. Chem. Soc. 1971, 93, 4332-4334. (b) Gravestock, M. B.; Johnson, W. S.; McCarry, B. E.; Parry, R. J.; Ratcliffe, B, E. J. Am. Chem. Soc. 1978, 100, 4274-4282. (c) Chapman, O. L.; Engel, M. R.; Springer, J. P.; Clardy, J. C. J. Am. Chem. Soc. 1971, 93, 6696-6698. (d) Nicolaou, K. C.; Petasis, N. A.; Zipkin, R. E. J. Am. Chem. Soc. 1982, 104, 5560-5562. (e) Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem. Soc. 1995, 117, 3448-3467. (f) Williams, D. R.; Coleman, P. J.; Henry, S. S. J. Am. Chem. Soc. 1993, 115, 11654-11655.
9. Proposed biosynthetic transformations have been reproduced in laboratory syntheses of natural products in order to test their practicality outside of the biological system and take advantage of the powerful transformations. Some examples include: (a) Johnson, W. S.; Gravestock, M. B.; McCarry, B. E. J. Am. Chem. Soc. 1971, 93, 4332-4334. (b) Gravestock, M. B.; Johnson, W. S.; McCarry, B. E.; Parry, R. J.; Ratcliffe, B, E. J. Am. Chem. Soc. 1978, 100, 4274-4282. (c) Chapman, O. L.; Engel, M. R.; Springer, J. P.; Clardy, J. C. J. Am. Chem. Soc. 1971, 93, 6696- 6698. (d) Nicolaou, K. C.; Petasis, N. A.; Zipkin, R. E. J. Am. Chem. Soc. 1982, 104, 5560-5562. (e) Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem. Soc. 1995, 117, 3448-3467. (f) Williams, D. R.; Coleman, P. J.; Henry, S. S. J. Am. Chem. Soc. 1993, 115, 11654-11655.
10. Proposed biosynthetic transformations have been reproduced in laboratory syntheses of natural products in order to test their practicality outside of the biological system and take advantage of the powerful transformations. Some examples include: (a) Johnson, W. S.; Gravestock, M. B.; McCarry, B. E. J. Am. Chem. Soc. 1971, 93, 4332-4334. (b) Gravestock, M. B.; Johnson, W. S.; McCarry, B. E.; Parry, R. J.; Ratcliffe, B, E. J. Am. Chem. Soc. 1978, 100, 4274-4282. (c) Chapman, O. L.; Engel, M. R.; Springer, J. P.; Clardy, J. C. J. Am. Chem. Soc. 1971, 93, 6696- 6698. (d) Nicolaou, K. C.; Petasis, N. A.; Zipkin, R. E. J. Am. Chem. Soc. 1982, 104, 5560-5562. (e) Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem. Soc. 1995, 117, 3448-3467. (f) Williams, D. R.; Coleman, P. J.; Henry, S. S. J. Am. Chem. Soc. 1993, 115, 11654-11655.
11. Proposed biosynthetic transformations have been reproduced in laboratory syntheses of natural products in order to test their practicality outside of the biological system and take advantage of the powerful transformations. Some examples include: (a) Johnson, W. S.; Gravestock, M. B.; McCarry, B. E. J. Am. Chem. Soc. 1971, 93, 4332-4334. (b) Gravestock, M. B.; Johnson, W. S.; McCarry, B. E.; Parry, R. J.; Ratcliffe, B, E. J. Am. Chem. Soc. 1978, 100, 4274-4282. (c) Chapman, O. L.; Engel, M. R.; Springer, J. P.; Clardy, J. C. J. Am. Chem. Soc. 1971, 93, 6696- 6698. (d) Nicolaou, K. C.; Petasis, N. A.; Zipkin, R. E. J. Am. Chem. Soc. 1982, 104, 5560-5562. (e) Evans, D. A.; Ratz, A. M.; Huff, B. E.; Sheppard, G. S. J. Am. Chem. Soc. 1995, 117, 3448-3467. (f) Williams, D. R.; Coleman, P. J.; Henry, S. S. J. Am. Chem. Soc. 1993, 115, 11654-11655.
12. Higa, T.; Tanaka, J.; Komesu, M.; Gravalos, D. C.; Puentes, J. L. F.; Bernardinelli, G.; Jefford, C. W. J. Am. Chem. Soc. 1992, 114, 7587-7588.
13. Okazaki, T.; Kitahara, T.; Okami, Y. J. Antibiot. 1976, 29, 1019-1025.
14. Mynderse, J, S.; Moore, R. E. J. Org. Chem. 1978, 43, 2301-2303.
15. Zampella, A.; D'Auria, M. D.; Minale L.; Debitus, C.; Roussakis, C. J. Am. Chem. Soc. 1996, 118, 11085-11088.
16. (a) Otake, N.; Koenuma, M.; Miyamae, H.; Sato, S.; Saito, Y. Tetrahedron Lett. 1975, 4147-4150.
17. (b) Omura, S.; Shibata, M.; Machida, S.; Sawada, J.; Otake, N. J. Antibiot. 1976, 29, 15-20.
18. (c) Riche, C.; Pascard-Billy, C. J. Chem. Soc., Chem. Commun. 1975, 951-952.
19. Petit, G. R.; Gao, F.; Sengupta, D.; Coll, J. C.; Herald, C. L.; Doubek, D. L.; Schmidt, J. M.; Van Camp, J. R.; Rudloe, J. J.; Nieman, R. A. Tetrahedron 1991, 47, 3601-3610,
20. Progress toward the total synthesis of miyakolide has been reported: Yoshimitsu, T.; Song, J. J.; Wang, G.-Q.; Masamune, S. J. Org. Chem. 1997, 62, 8978-8979.
21. For recent reviews on the biosynthesis of polyketides, see: (a) Cortes, J.; Haydock, S. F.; Roberts, G. A.; Bevitt, D. J.; Leadlay, P. F. Nature 1990, 348, 176-178. (b) Donadio, S.; Staver, M. J.; McAlpine, J. B.; Swanson, S. J.; Katz, L. Science 1991, 252, 675-679. (c) Malpartida, F.; Hopwood, D. A. Nature 1984, 309, 462-464. (d) O'Hagan, D. Nat. Prod. Rep. 1995, 1-33.
22. For recent reviews on the biosynthesis of polyketides, see: (a) Cortes, J.; Haydock, S. F.; Roberts, G. A.; Bevitt, D. J.; Leadlay, P. F. Nature 1990, 348, 176-178. (b) Donadio, S.; Staver, M. J.; McAlpine, J. B.; Swanson, S. J.; Katz, L. Science 1991, 252, 675-679. (c) Malpartida, F.; Hopwood, D. A. Nature 1984, 309, 462-464. (d) O'Hagan, D. Nat. Prod. Rep. 1995, 1-33.
23. For recent reviews on the biosynthesis of polyketides, see: (a) Cortes, J.; Haydock, S. F.; Roberts, G. A.; Bevitt, D. J.; Leadlay, P. F. Nature 1990, 348, 176-178. (b) Donadio, S.; Staver, M. J.; McAlpine, J. B.; Swanson, S. J.; Katz, L. Science 1991, 252, 675-679. (c) Malpartida, F.; Hopwood, D. A. Nature 1984, 309, 462-464. (d) O'Hagan, D. Nat. Prod. Rep. 1995, 1-33.
24. For recent reviews on the biosynthesis of polyketides, see: (a) Cortes, J.; Haydock, S. F.; Roberts, G. A.; Bevitt, D. J.; Leadlay, P. F. Nature 1990, 348, 176-178. (b) Donadio, S.; Staver, M. J.; McAlpine, J. B.; Swanson, S. J.; Katz, L. Science 1991, 252, 675-679. (c) Malpartida, F.; Hopwood, D. A. Nature 1984, 309, 462-464. (d) O'Hagan, D. Nat. Prod. Rep. 1995, 1-33.
25. Transannular reactions have been postulated in a number of biosynthetic pathways. The dolabellanes are postulated to be biosynthetically converted to the clavularanes and dolastanes via transannular ring-contracting reactions: (a) Look, S. A.; Fenical, W. J. Org. Chem. 1982, 47, 4129-4134. Dactylol is postulated to be biosynthesized from humulene, via a ring-contracting cationic olefin cyclization followed by cyclopropyl cation rearrangement and solvolysis: (b) Schmitz, F. J.; Hollenbeak, K. H.; Vanderah, D. J. Tetrahedron 1978, 34, 2719-2722. (c) Hayasaka, K.; Ohtsuka, T.; Shirahama, H. Tetrahedron Lett. 1985, 26, 873-876. The endiandric acids are postulated to be biosynthesized via a cascade of electrocyclic reactions, including a ring-contracting cyclization: (d) Bandaranayake, W. M.; Banfield, J. E.; Black, D. St. C. J. Chem. Soc., Chem. Commun. 1980, 902-903.
26. Transannular reactions have been postulated in a number of biosynthetic pathways. The dolabellanes are postulated to be biosynthetically converted to the clavularanes and dolastanes via transannular ring- contracting reactions: (a) Look, S. A.; Fenical, W. J. Org. Chem. 1982, 47, 4129-4134. Dactylol is postulated to be biosynthesized from humulene, via a ring-contracting cationic olefin cyclization followed by cyclopropyl cation rearrangement and solvolysis: (b) Schmitz, F. J.; Hollenbeak, K. H.; Vanderah, D. J. Tetrahedron 1978, 34, 2719-2722. (c) Hayasaka, K.; Ohtsuka, T.; Shirahama, H. Tetrahedron Lett. 1985, 26, 873-876. The endiandric acids are postulated to be biosynthesized via a cascade of electrocyclic reactions, including a ring-contracting cyclization: (d) Bandaranayake, W. M.; Banfield, J. E.; Black, D. St. C. J. Chem. Soc., Chem. Commun. 1980, 902-903.
27. Transannular reactions have been postulated in a number of biosynthetic pathways. The dolabellanes are postulated to be biosynthetically converted to the clavularanes and dolastanes via transannular ring- contracting reactions: (a) Look, S. A.; Fenical, W. J. Org. Chem. 1982, 47, 4129-4134. Dactylol is postulated to be biosynthesized from humulene, via a ring-contracting cationic olefin cyclization followed by cyclopropyl cation rearrangement and solvolysis: (b) Schmitz, F. J.; Hollenbeak, K. H.; Vanderah, D. J. Tetrahedron 1978, 34, 2719-2722. (c) Hayasaka, K.; Ohtsuka, T.; Shirahama, H. Tetrahedron Lett. 1985, 26, 873-876. The endiandric acids are postulated to be biosynthesized via a cascade of electrocyclic reactions, including a ring-contracting cyclization: (d) Bandaranayake, W. M.; Banfield, J. E.; Black, D. St. C. J. Chem. Soc., Chem. Commun. 1980, 902-903.
28. Transannular reactions have been postulated in a number of biosynthetic pathways. The dolabellanes are postulated to be biosynthetically converted to the clavularanes and dolastanes via transannular ring- contracting reactions: (a) Look, S. A.; Fenical, W. J. Org. Chem. 1982, 47, 4129-4134. Dactylol is postulated to be biosynthesized from humulene, via a ring-contracting cationic olefin cyclization followed by cyclopropyl cation rearrangement and solvolysis: (b) Schmitz, F. J.; Hollenbeak, K. H.; Vanderah, D. J. Tetrahedron 1978, 34, 2719-2722. (c) Hayasaka, K.; Ohtsuka, T.; Shirahama, H. Tetrahedron Lett. 1985, 26, 873-876. The endiandric acids are postulated to be biosynthesized via a cascade of electrocyclic reactions, including a ring-contracting cyclization: (d) Bandaranayake, W. M.; Banfield, J. E.; Black, D. St. C. J. Chem. Soc., Chem. Commun. 1980, 902-903.
29. Macrocyclic conformation has been employed as a control element in synthesis in several instances: (a) Still, W. C.; Romero, A. G. J. Am. Chem. Soc. 1986, 108, 2105-2106. (b) Schreiber, S. L.; Sammakia, T.; Hulin, B.; Schulte, G. J. Am. Chem. Soc. 1986, 108, 2106-2108. (c) Vedejs, E.; Gapinski, D. M. J. Am. Chem. Soc. 1983, 105, 5058-5061. Macrocyclic ring contractions have been used with success to control diastereoselectivity of the contracted ring-forming reaction, (d) Myers, A. G.; Condroski, K. R. J. Am. Chem. Soc. 1993, 115, 7926-7927.
30. Macrocyclic conformation has been employed as a control element in synthesis in several instances: (a) Still, W. C.; Romero, A. G. J. Am. Chem. Soc. 1986, 108, 2105-2106. (b) Schreiber, S. L.; Sammakia, T.; Hulin, B.; Schulte, G. J. Am. Chem. Soc. 1986, 108, 2106-2108. (c) Vedejs, E.; Gapinski, D. M. J. Am. Chem. Soc. 1983, 105, 5058-5061. Macrocyclic ring contractions have been used with success to control diastereoselectivity of the contracted ring-forming reaction, (d) Myers, A. G.; Condroski, K. R. J. Am. Chem. Soc. 1993, 115, 7926-7927.
31. Macrocyclic conformation has been employed as a control element in synthesis in several instances: (a) Still, W. C.; Romero, A. G. J. Am. Chem. Soc. 1986, 108, 2105-2106. (b) Schreiber, S. L.; Sammakia, T.; Hulin, B.; Schulte, G. J. Am. Chem. Soc. 1986, 108, 2106-2108. (c) Vedejs, E.; Gapinski, D. M. J. Am. Chem. Soc. 1983, 105, 5058-5061. Macrocyclic ring contractions have been used with success to control diastereoselectivity of the contracted ring-forming reaction, (d) Myers, A. G.; Condroski, K. R. J. Am. Chem. Soc. 1993, 115, 7926-7927.
32. Macrocyclic conformation has been employed as a control element in synthesis in several instances: (a) Still, W. C.; Romero, A. G. J. Am. Chem. Soc. 1986, 108, 2105-2106. (b) Schreiber, S. L.; Sammakia, T.; Hulin, B.; Schulte, G. J. Am. Chem. Soc. 1986, 108, 2106-2108. (c) Vedejs, E.; Gapinski, D. M. J. Am. Chem. Soc. 1983, 105, 5058-5061. Macrocyclic ring contractions have been used with success to control diastereoselectivity of the contracted ring-forming reaction, (d) Myers, A. G.; Condroski, K. R. J. Am. Chem. Soc. 1993, 115, 7926-7927.
33. 13 atom distance of 4.5 Å or less that were generated three or more times during the search (out of 150, 000 structures generated) were considered. The AMBER force field was selected because it generated a minimized structure of miyakolide that more closely fit the X-ray crystal structure than structures generated using the MM2 and MM3 force fields.
34. For a review on the use of isoxazoles in synthesis, see: (a) Baraldi, P. G.; Barco, A.; Benetti, S.; Pollini, G. P.; Simoni, D. Synthesis 1987, 857-869. (b) Little, R. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991 ; Vol. 5 pp 239- 270. (c) Torssell, K. B. G. Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis; VCH Publishers: New York, 1988. (d) Caramella, P.; Grunanger, P. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley & Sons: New York, 1984; Vol. 1, pp 291-392.
35. For a review on the use of isoxazoles in synthesis, see: (a) Baraldi, P. G.; Barco, A.; Benetti, S.; Pollini, G. P.; Simoni, D. Synthesis 1987, 857-869. (b) Little, R. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991 ; Vol. 5 pp 239-270. (c) Torssell, K. B. G. Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis; VCH Publishers: New York, 1988. (d) Caramella, P.; Grunanger, P. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley & Sons: New York, 1984; Vol. 1, pp 291-392.
36. For a review on the use of isoxazoles in synthesis, see: (a) Baraldi, P. G.; Barco, A.; Benetti, S.; Pollini, G. P.; Simoni, D. Synthesis 1987, 857-869. (b) Little, R. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991 ; Vol. 5 pp 239- 270. (c) Torssell, K. B. G. Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis; VCH Publishers: New York, 1988. (d) Caramella, P.; Grunanger, P. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley & Sons: New York, 1984; Vol. 1, pp 291-392.
37. For a review on the use of isoxazoles in synthesis, see: (a) Baraldi, P. G.; Barco, A.; Benetti, S.; Pollini, G. P.; Simoni, D. Synthesis 1987, 857-869. (b) Little, R. D. In Comprehensive Organic Synthesis; Trost, B. M., Fleming, I., Eds.; Pergamon Press: New York, 1991 ; Vol. 5 pp 239- 270. (c) Torssell, K. B. G. Nitrile Oxides, Nitrones, and Nitronates in Organic Synthesis; VCH Publishers: New York, 1988. (d) Caramella, P.; Grunanger, P. In 1,3-Dipolar Cycloaddition Chemistry; Padwa, A., Ed.; John Wiley & Sons: New York, 1984; Vol. 1, pp 291-392.
38. Although deprotonation of an enaminone (NaOH) was required to promote an aldol reaction (Yuste, F.; Sanchez-Obregon, R. J. Org. Chem. 1982, 47, 3665-3668), we hoped that the intramolecularity of our transformation would force the reacting partners together and facilitate a reaction under milder conditions.
39. 16 stereocenter.
40. (a) Kato, N.; Hamada, Y.; Shioiri, T. Chem. Pharm. Bull. 1984, 32, 1679-1682.
41. (b) Eiden, F.; Patzelt, G. Arch. Pharm. (Weinheim, Ger.) 1986, 319, 242-251.
42. (c) Auricchio, S.; Ricca, A.; DePava, O. V. Gazz. Chim. Ital. 1980, 110, 567-570.
43. (d) Kobuke, Y.; Kokubo, K.; Munakata, M. J. Am. Chem. Soc. 1995, 117, 12751-12758.
44. (e) Kashima, C.; Mukai, N.; Tsuda, Y. Chem. Lett. 1973, 539-540.
45. 4) and water in a variety of organic solvents.
46. Evans, D. A.; Ripin D. H. B.; Johnson, J. S.; Shaughnessy, E. A. Angew. Chem., Int. Ed. Engl. 1997, 36, 2119-2121.
47. (a) Evans, D. A.; Clark, J. S.; Metternich, R.; Novack, V. J.; Sheppard, G. S. J. Am. Chem. Soc. 1990, 112, 866-868.
48. (b) Evans, D. A.; Ng, H. P.; Clark, J. S.; Rieger, D. L. Tetrahedron 1992, 2127-2142.
49. For a review, see: Boutagy, J.; Thomas, R. Chem. Rev. 1974, 74, 87-99.
50. (a) Peterson, D. J. J. Org. Chem. 1968, 33, 780-784.
51. (b) Shimoji, K.; Taguchi, H.; Oshima, K.; Yamamoto, H.; Nozaki, H. J. Am. Chem. Soc. 1974, 96, 1620-1621.
52. A β-ketoimide has been employed in an analogous intramolecular ketaliation without epimerization of the α-stereocenter in a synthesis of lonomycin (ref 3e).
53. Brownbridge, P.; Chan, T. H.; Brook, M. A.; Kang, G. J. Can. J. Chem. 1983, 61, 688-693.
54. Hendrickson, H. S.; Hendrickson, E. K. Chem. Phys. Lipids 1990, 53, 115-120.
55. Mancuso, A. J.; Swern, D. Synthesis 1981, 165-185.
56. Evans, D. A.; Gage, J. R.; Leighton, J. L. J. Am. Chem. Soc. 1992, 114, 9434-9453.
57. (a) Izawa, T.; Mukaiyama, T. Chem. Lett. 1978, 409-412.
58. (b) Hagiwara, H.; Kimura, K.; Uda, H. J. Chem. Soc., Perkins Trans. 1 1992, 693-700.
59. Chen, K.-M.; Hardtmann, G. E.; Prasad, K.; Repic, O.; Shapiro, M. J. Tetrahedron Lett. 1987, 28, 155-158.
60. 5 to mask the exocyclic enoate.
61. Zakharkin, L. I.; Khorlina, I. M. Tetrahedron Lett. 1962, 619-620.
62. (a) Evans, D. A.; Bartroli, J.; Shih, T. L. J. Am. Chem. Soc. 1981, 103, 2127-2129.
63. (b) Gage, J. R.; Evans, D. A. Org. Synth. 1989, 68, 77-82.
64. Evans, D. A.; Chapman, K. T.; Carreira, E. M. J. Am. Chem. Soc. 1988, 110, 3560-3578.
65. Oikawa, Y.; Yoshioka, T.; Yonemitsu, O. Tetrahedron Lett. 1982, 23, 885-888.
66. Trapping of the lithium and sodium enolates used for the olefinations with TBSOTf gave identical silyl ketene acetals.
67. 2O, 0°C) was sluggish; a large excess of LiOOH at rt was required to achieve completion and competitive hydrolysis of the unsaturated ester was observed,
68. (b) Evans, D. A.; Britton, T. C.; Ellman, J. A. Tetrahedron Lett. 1987, 28, 6141-6144.
69. Evans, D. A.; Bilodeau, M. T.; Somers, T. C.; Clardy, J.; Cherry, D.; Kato, Y. J. Org. Chem. 1991, 56, 5750-5752.
70. (a) Penning, T. D.; Djuric, S. W.; Haack, R. A.; Kalish, V. J.; Miyashiro, J. M.; Rowell, B. W.; Yu, S. S. Synth. Commun. 1990, 307-312.
71. (b) Kim, A. S. Ph.D. Thesis, Harvard University, 1996.
72. Corey, E. J.; Fuchs, P. L. Tetrahedron Lett. 1972, 3769-3972.
73. Parikh, J. R.; Doering, W. v. E. J. Am. Chem. Soc. 1967, 89, 5505-5507.
74. Paterson, I.; Goodman, J. M.; Isaka, M. Tetrahedron Lett. 1989, 30, 7121-7124.
75. (a) Freeman, P. K.; Hutchinson, L. L. J. Org. Chem. 1980, 45, 1924-1930.
76. (b) Ireland, R. E.; Smith, M. G. J. Am. Chem. Soc. 1988, 110, 854-860.
77. Blanchette, M. A.; Choy, W.; Davis, J. T.; Essenfield, A. P.; Masamune, S.; Roush, W. R.; Sakai, T. Tetrahedron Lett. 1984, 25, 2183-2186.
78. Evans, D. A.; Carreira, E. M. Tetrahedron Lett. 1990, 31, 4703-4706.
79. 2 + bP. See the Experimental Section for details.
80. Chlorinating agents tried included isocyanuric chloride, tert-butyl hypochlorite at -78°C (ref 48a), NCS (ref 48b, c), and NaOCl in a biphasic system (ref 48d, e).
81. (a) Stevens, R. V.; Beaulieu, N.; Chan, W. H.; Daniewski, A. R.; Takeda, T.; Waldner, A.; Williard, P. G.; Zutter, U. J. Am. Chem. Soc. 1986, 108, 1039-1049.
82. (b) Stevens, R. V. Tetrahedron 1976, 32, 1599-1612.
83. (c) Liu, K.-C.; Shelton, B. R.; Howe, R. K. J. Org. Chem. 1980, 45, 3916-3918.
84. (d) Ponzio, G.; Busti, G. Gazz. Chim. Ital. II 1906, 36, 338.
85. (e) Grundmann, C.; Datta, S. K. J. Org. Chem. 1969, 34, 2016-2018.
86. (a) Kornblum, N.; Taub, B.; Ungnade, H. E. J. Am. Chem. Soc. 1954, 76, 3209-3211.
87. (b) Komblum, N.; Ungnade, H. E. Organic Syntheses; Wiley: New York, 1963; Collect. Vol. IV, pp 724-727.
88. For examples, see: (a) Evans, D. A.; DiMare, M. J. Am. Chem. Soc. 1986, 108, 2476-2478. (b) Evans, D. A.; Ng, H. P.; Rieger, D. L. J. Am. Chem. Soc. 1993, 115, 11446-11459. (c) Evans, D. A.; Kim, A. S. J. Am. Chem. Soc. 1996, 118, 11323-11324.
89. For examples, see: (a) Evans, D. A.; DiMare, M. J. Am. Chem. Soc. 1986, 108, 2476-2478. (b) Evans, D. A.; Ng, H. P.; Rieger, D. L. J. Am. Chem. Soc. 1993, 115, 11446-11459. (c) Evans, D. A.; Kim, A. S. J. Am. Chem. Soc. 1996, 118, 11323-11324.
90. For examples, see: (a) Evans, D. A.; DiMare, M. J. Am. Chem. Soc. 1986, 108, 2476-2478. (b) Evans, D. A.; Ng, H. P.; Rieger, D. L. J. Am. Chem. Soc. 1993, 115, 11446-11459. (c) Evans, D. A.; Kim, A. S. J. Am. Chem. Soc. 1996, 118, 11323-11324.
91. Mukiyama, T.; Hoshino, T. J. Am. Chem. Soc. 1960, 82, 5339-5342.
92. Damon, R. E.; Coppola, G. M. Tetrahedron Lett. 1990, 31, 2849-2852.
93. (a) Corey, E. J.; Bock, M. C. Tetrahedron Lett. 1975, 3269-3270.
94. (b) Schwyzer, R.; Hurlimann, C. Helv. Chim. Acta 1954, 18, 155-166.
95. Since nitrile oxides readily dimerize to furoxans (ref 15c), they must be generated at low concentration in the presence of the efficient dipolarophile.
96. 5 resonance at δ 8.40. The Aldrich Library of NMR Spectra, Edition II; Pouchert, C. J., Ed.; Aldrich Chemical Co.: Milwaukee, WI, 1983; Vol. 2, p 503.
97. Sakaitani, M.; Kurokawa, N.; Ohfune, Y. Tetrahedron Lett. 1986, 27, 3753-3754.
98. The breakdown of the intermediate triethylsilyl ester required exposure to silica gel (chromatography) to reveal the highly polar diol acid. Recovering the acid from silica gel was difficult, and the silyl ester hydrolysis efficiency decreased as loading on silica gel increased. The desired diol acid proved extremely acid sensitive, and an efficient alternative cleavage of the TES ester was not found.
99. Felix, A. M.; Heimer, E. P.; Lambros, T. J.; Tzougraki, C.; Meienhofer, J. J. Org. Chem. 1978, 43, 4194-4196.
100. Inanaga, J.; Hirata, K.; Saeki, H.; Katsuki, T.; Yamaguchi, M. Bull. Chem. Soc. Jpn. 1979, 52, 1989-1993.
101. Macrolactonization via intramolecular [3 + 2] cycloaddition has been demonstrated to be highly selective and efficient. Ko, S. S.; Confalone, P. N. Tetrahedron 1985, 41, 3511-3518.
102. Excess alcohol 43 was converted to its 2,4,6-trichlotobenzoate ester. All other esterification conditions investigated (EDC (ref 62a-c), diisopropylcarbodiimide (ref 62a-c), PyBrOP (ref 62d), and BOP-Cl (ref 62e)) failed to deliver any esterified product.
103. (a) Sheehan, J. C.; Hess, G. P. J. Am. Chem. Soc. 1955, 77, 1067-1068.
104. (b) Cruickshank, P. A.; Sheehan, J. C. J. Org. Chem. 1961, 26, 2525-2528.
105. (c) Hegarty, A. F.; Bruice, T. C. J. Am. Chem. Soc. 1970, 92, 6568-6574.
106. (d) Castro, B.; Coste, J. Fr. Patent 89-02-361.
107. (e) Diago-Meseguer, J.; Palomo-Coll, A. L.; Fernandez-Lizarbe, J. R.; Zugaza-Bilbao, A. Synthesis 1980, 547-551.
108. Stagno D'Alcontres, G. Gazz. Chim. Ital. 1950, 80, 441.
109. Nitta, M.; Kobayashi, T. J. Chem. Soc., Chem. Commun 1982, 877-878.
110. Kashima, C.; Katoh, A.; Yokota, Y.; Omote, Y. Synthesis 1983, 151-153.
111. 2 + bP. See the Experimental Section (Supporting Information) for details.