Biomimetic synthesis of fused polypyrans: Oxacyclization stereo- and regioselectivity is a function of the nucleophile

Organic Letters

Volumn 5, Issue 12, 2003, Pages 2123-2126

  Bravo, Fernando ^a   McDonald, Frank E ^a   Neiwert, Wade A ^a   Do, Bao ^a   Hardcastle, Kenneth I ^a  

^a EMORY UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CARBAMIC ACID DERIVATIVE; EPOXIDE; LEWIS ACID; PYRAN DERIVATIVE;

ARTICLE; BIOMIMETICS; CYCLIZATION; STEREOCHEMISTRY; SUBSTITUTION REACTION; SYNTHESIS;

BIOMIMETICS; CYCLIZATION; EPOXY COMPOUNDS; MODELS, MOLECULAR; PYRANS; STEREOISOMERISM;

EID: 0141630583     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol034539o     Document Type: Article

References (49)

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6. Total syntheses of hemibrevetoxin B: (a) Nicolaou, K. C.; Raja Reddy, K. ; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558. (b) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777. (c) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365. (d) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557. (e) Kadota, I.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6597. (f) Rainier, J. D.; Allwein, S. P.; Cox, J. M. J. Org. Chem. 2001, 66, 1380.
7. Total syntheses of hemibrevetoxin B: (a) Nicolaou, K. C.; Raja Reddy, K. ; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558. (b) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777. (c) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365. (d) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557. (e) Kadota, I.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6597. (f) Rainier, J. D.; Allwein, S. P.; Cox, J. M. J. Org. Chem. 2001, 66, 1380.
8. Total syntheses of hemibrevetoxin B: (a) Nicolaou, K. C.; Raja Reddy, K. ; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558. (b) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777. (c) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365. (d) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557. (e) Kadota, I.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6597. (f) Rainier, J. D.; Allwein, S. P.; Cox, J. M. J. Org. Chem. 2001, 66, 1380.
9. Total syntheses of hemibrevetoxin B: (a) Nicolaou, K. C.; Raja Reddy, K. ; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558. (b) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777. (c) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365. (d) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557. (e) Kadota, I.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6597. (f) Rainier, J. D.; Allwein, S. P.; Cox, J. M. J. Org. Chem. 2001, 66, 1380.
10. Total syntheses of hemibrevetoxin B: (a) Nicolaou, K. C.; Raja Reddy, K. ; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558. (b) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777. (c) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365. (d) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557. (e) Kadota, I.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6597. (f) Rainier, J. D.; Allwein, S. P.; Cox, J. M. J. Org. Chem. 2001, 66, 1380.
11. Total syntheses of hemibrevetoxin B: (a) Nicolaou, K. C.; Raja Reddy, K. ; Skokotas, G.; Sato, F.; Xiao, X.-Y.; Hwang, C.-K. J. Am. Chem. Soc. 1993, 115, 3558. (b) Kadota, I.; Jung-Youl, P.; Koumura, N.; Pollaud, G.; Matsukawa, Y.; Yamamoto, Y. Tetrahedron Lett. 1995, 36, 5777. (c) Morimoto, M.; Matsukura, H.; Nakata, T. Tetrahedron Lett. 1996, 37, 6365. (d) Mori, Y.; Yaegashi, K.; Furukawa, H. J. Am. Chem. Soc. 1997, 119, 4557. (e) Kadota, I.; Yamamoto, Y. J. Org. Chem. 1998, 63, 6597. (f) Rainier, J. D.; Allwein, S. P.; Cox, J. M. J. Org. Chem. 2001, 66, 1380.
12. Total synthesis of brevetoxin B: (a) Nicolaou, K. C.; Theodorakis, E. A. ; Rutjes, F. P. J. T.; Tiebes, J.; Sato, M.; Untersteller, E.; Xiao,X.-Y. J. Am. Chem. Soc. 1995, 117, 1171. (b) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 1173. (c) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E.; Nugiel, D. A.; Abe, Y.; Reddy, K. B.; DeFrees, S. A.; Reddy, D. R.; Awartani, R. A.; Conley, S. R.; Rutjes, F. P. J. T.; Theodorakis, E. A. J. Am. Chem. Soc. 1995, 117, 10227. (d) Nicolaou, K. C.; Theodorakis, E. A.; Rutjes, F. P. J. T.; Sato, M.; Tiebes, J.; Xiao, X.-Y.; Hwang, C.-K.; Duggan, M. E.; Yang, Z.; Couladouros, E. A.; Sato, F.; Shin, J.; He, H.-M.; Bleckman, T. J. Am. Chem. Soc. 1995, 117, 10239. (e) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 10252.
13. Total synthesis of brevetoxin B: (a) Nicolaou, K. C.; Theodorakis, E. A. ; Rutjes, F. P. J. T.; Tiebes, J.; Sato, M.; Untersteller, E.; Xiao,X.-Y. J. Am. Chem. Soc. 1995, 117, 1171. (b) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 1173. (c) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E.; Nugiel, D. A.; Abe, Y.; Reddy, K. B.; DeFrees, S. A.; Reddy, D. R.; Awartani, R. A.; Conley, S. R.; Rutjes, F. P. J. T.; Theodorakis, E. A. J. Am. Chem. Soc. 1995, 117, 10227. (d) Nicolaou, K. C.; Theodorakis, E. A.; Rutjes, F. P. J. T.; Sato, M.; Tiebes, J.; Xiao, X.-Y.; Hwang, C.-K.; Duggan, M. E.; Yang, Z.; Couladouros, E. A.; Sato, F.; Shin, J.; He, H.-M.; Bleckman, T. J. Am. Chem. Soc. 1995, 117, 10239. (e) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 10252.
14. Total synthesis of brevetoxin B: (a) Nicolaou, K. C.; Theodorakis, E. A. ; Rutjes, F. P. J. T.; Tiebes, J.; Sato, M.; Untersteller, E.; Xiao,X.-Y. J. Am. Chem. Soc. 1995, 117, 1171. (b) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 1173. (c) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E.; Nugiel, D. A.; Abe, Y.; Reddy, K. B.; DeFrees, S. A.; Reddy, D. R.; Awartani, R. A.; Conley, S. R.; Rutjes, F. P. J. T.; Theodorakis, E. A. J. Am. Chem. Soc. 1995, 117, 10227. (d) Nicolaou, K. C.; Theodorakis, E. A.; Rutjes, F. P. J. T.; Sato, M.; Tiebes, J.; Xiao, X.-Y.; Hwang, C.-K.; Duggan, M. E.; Yang, Z.; Couladouros, E. A.; Sato, F.; Shin, J.; He, H.-M.; Bleckman, T. J. Am. Chem. Soc. 1995, 117, 10239. (e) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 10252.
15. Total synthesis of brevetoxin B: (a) Nicolaou, K. C.; Theodorakis, E. A. ; Rutjes, F. P. J. T.; Tiebes, J.; Sato, M.; Untersteller, E.; Xiao,X.-Y. J. Am. Chem. Soc. 1995, 117, 1171. (b) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 1173. (c) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E.; Nugiel, D. A.; Abe, Y.; Reddy, K. B.; DeFrees, S. A.; Reddy, D. R.; Awartani, R. A.; Conley, S. R.; Rutjes, F. P. J. T.; Theodorakis, E. A. J. Am. Chem. Soc. 1995, 117, 10227. (d) Nicolaou, K. C.; Theodorakis, E. A.; Rutjes, F. P. J. T.; Sato, M.; Tiebes, J.; Xiao, X.-Y.; Hwang, C.-K.; Duggan, M. E.; Yang, Z.; Couladouros, E. A.; Sato, F.; Shin, J.; He, H.-M.; Bleckman, T. J. Am. Chem. Soc. 1995, 117, 10239. (e) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 10252.
16. Total synthesis of brevetoxin B: (a) Nicolaou, K. C.; Theodorakis, E. A. ; Rutjes, F. P. J. T.; Tiebes, J.; Sato, M.; Untersteller, E.; Xiao,X.-Y. J. Am. Chem. Soc. 1995, 117, 1171. (b) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 1173. (c) Nicolaou, K. C.; Hwang, C.-K.; Duggan, M. E.; Nugiel, D. A.; Abe, Y.; Reddy, K. B.; DeFrees, S. A.; Reddy, D. R.; Awartani, R. A.; Conley, S. R.; Rutjes, F. P. J. T.; Theodorakis, E. A. J. Am. Chem. Soc. 1995, 117, 10227. (d) Nicolaou, K. C.; Theodorakis, E. A.; Rutjes, F. P. J. T.; Sato, M.; Tiebes, J.; Xiao, X.-Y.; Hwang, C.-K.; Duggan, M. E.; Yang, Z.; Couladouros, E. A.; Sato, F.; Shin, J.; He, H.-M.; Bleckman, T. J. Am. Chem. Soc. 1995, 117, 10239. (e) Nicolaou, K. C.; Rutjes, F. P. J. T.; Theodorakis, E. A.; Tiebes, J.; Sato, M.; Untersteller, E. J. Am. Chem. Soc. 1995, 117, 10252.
17. Total synthesis of brevetoxin A: (a) Nicolaou, K. C.; Bunnage, M. E., McGarry, D. G.; Shi, S.; Somers, P. K.; Wallace, P. A.; Chu, X.-J.; Agrios, K. A.; Gunzner, J. L.; Yang, Z. Chem. Eur. J. 1999, 5, 599. (b) Nicolaou, K. C.; Wallace, P. A.; Shi, S.; Ouellette, M. A.; Bunnage, M. E.; Gunzner, J. L.; Agrios, K. A.; Shi, G.-Q.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 618. (c) Nicolaou, K. C.; Shi, G.-Q.; Gunzner, J. L.; Gartner, P.; Wallace, P. A.; Ouellette, M. A.; Shi, S.; Bunnage, M. E.; Agrios, K. A.; Veale, C. A.; Hwang, C.-K.; Hutchinson, J.; Prasad, C. V. C.; Ogilvie, W. W.; Yang, Z. Chem. Eur. J. 1999, 5, 628. (d) Nicolaou, K. C.; Gunzner, J. L.; Shi, G.-Q.; Agrios, K. A.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 646.
18. Total synthesis of brevetoxin A: (a) Nicolaou, K. C.; Bunnage, M. E., McGarry, D. G.; Shi, S.; Somers, P. K.; Wallace, P. A.; Chu, X.-J.; Agrios, K. A.; Gunzner, J. L.; Yang, Z. Chem. Eur. J. 1999, 5, 599. (b) Nicolaou, K. C.; Wallace, P. A.; Shi, S.; Ouellette, M. A.; Bunnage, M. E.; Gunzner, J. L.; Agrios, K. A.; Shi, G.-Q.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 618. (c) Nicolaou, K. C.; Shi, G.-Q.; Gunzner, J. L.; Gartner, P.; Wallace, P. A.; Ouellette, M. A.; Shi, S.; Bunnage, M. E.; Agrios, K. A.; Veale, C. A.; Hwang, C.-K.; Hutchinson, J.; Prasad, C. V. C.; Ogilvie, W. W.; Yang, Z. Chem. Eur. J. 1999, 5, 628. (d) Nicolaou, K. C.; Gunzner, J. L.; Shi, G.-Q.; Agrios, K. A.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 646.
19. Total synthesis of brevetoxin A: (a) Nicolaou, K. C.; Bunnage, M. E., McGarry, D. G.; Shi, S.; Somers, P. K.; Wallace, P. A.; Chu, X.-J.; Agrios, K. A.; Gunzner, J. L.; Yang, Z. Chem. Eur. J. 1999, 5, 599. (b) Nicolaou, K. C.; Wallace, P. A.; Shi, S.; Ouellette, M. A.; Bunnage, M. E.; Gunzner, J. L.; Agrios, K. A.; Shi, G.-Q.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 618. (c) Nicolaou, K. C.; Shi, G.-Q.; Gunzner, J. L.; Gartner, P.; Wallace, P. A.; Ouellette, M. A.; Shi, S.; Bunnage, M. E.; Agrios, K. A.; Veale, C. A.; Hwang, C.-K.; Hutchinson, J.; Prasad, C. V. C.; Ogilvie, W. W.; Yang, Z. Chem. Eur. J. 1999, 5, 628. (d) Nicolaou, K. C.; Gunzner, J. L.; Shi, G.-Q.; Agrios, K. A.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 646.
20. Total synthesis of brevetoxin A: (a) Nicolaou, K. C.; Bunnage, M. E., McGarry, D. G.; Shi, S.; Somers, P. K.; Wallace, P. A.; Chu, X.-J.; Agrios, K. A.; Gunzner, J. L.; Yang, Z. Chem. Eur. J. 1999, 5, 599. (b) Nicolaou, K. C.; Wallace, P. A.; Shi, S.; Ouellette, M. A.; Bunnage, M. E.; Gunzner, J. L.; Agrios, K. A.; Shi, G.-Q.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 618. (c) Nicolaou, K. C.; Shi, G.-Q.; Gunzner, J. L.; Gartner, P.; Wallace, P. A.; Ouellette, M. A.; Shi, S.; Bunnage, M. E.; Agrios, K. A.; Veale, C. A.; Hwang, C.-K.; Hutchinson, J.; Prasad, C. V. C.; Ogilvie, W. W.; Yang, Z. Chem. Eur. J. 1999, 5, 628. (d) Nicolaou, K. C.; Gunzner, J. L.; Shi, G.-Q.; Agrios, K. A.; Gartner, P.; Yang, Z. Chem. Eur. J. 1999, 5, 646.
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24. Total synthesis of gambierol: (a) Fuwa, H.; Sasaki, M.; Satake, M.; Tachibana, K. Org. Lett. 2002, 4, 2981. (b) Fuwa, H.; Kainuma, N.; Tachibana, K.; Sasaki, M. J. Am. Chem. Soc. 2002, 124, 14983. (c) Kadota, I.; Takamura, H. ; Sato, K.; Ohno, A.; Matsuda, K.; Yamamoto, Y. J. Am. Chem. Soc. 2003, 125, 46.
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30. 3-promoted endo-selective oxacyclization to trans-syn-trans-fused his- and tristetrahydropyrans. However, regioselective oxacyclization requires the presence of chelating alkoxymethyl substituents at each epoxide, which adds an undesirable degree of complexity to substrate synthesis as well as product structures, which are also produced in yields lower than those generally reported by our strategy. See: Tokiwano, T.; Fujiwara, K.; Murai, A. Synlett 2000, 335.
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33. A minor modification was introduced from the procedure described in ref 10a: the reaction of isoprene with tert-butyl hypochlorite in acetic acid at -10°C gave directly the 1,4 addition of chlorine and acetate in 99:1 E/Z ratio (GC/MS).
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35. The enantioselectivity was determined to be 95:5 er for the benzoate derivative of 2 by HPLC analysis. See the Supporting Information for details.
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40. Basel, Y.;Hassner, A. J. Org. Chem. 2000, 65, 6368.
41. See the Supporting Information for essential data and thermal ellipsoid diagrams for compounds 10-12 and 18. The detailed crystallographic data can be obtained from the Cambridge Crystallographic Data Center (CCDC) free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html. Compound 10: CCDC 202087. Compound 11: CCDC 202085. Compound 12: CCDC 202086. Compound 18: CCDC 202088.
42. 1H NMR from cyclization of 7.
43. 2. Compounds 7-9 were prepared by reacting a THF solution of 3 with either n-BuLi (for 7) or Nail (for 8 and 9) and the corresponding carbamoyl chloride.
44. Temperatures for the cyclizations of 4 and 7 were optimized by exploring a range from -95 to +40°C, with only the best results shown in the tables. Although formation of the tert-butyl ether byproduct 12 relative to alcohol 11 is diminished at higher temperatures, the stereo- and regioselectivity for fused bicyclic products 11 and 12 vs byproducts i and ii remains constant. For cyclizations of 7, optimized results are obtained with a short reaction time (Table 1, entry 6), as more side products are formed with the longer reaction times required for lower temperature experiments.
45. (a) Sneen, R. A. Acc. Chem. Res. 1973, 6, 46.
46. (b) Jencks, W. P. Acc. Chem. Res. 1980, 13, 161. We thank Prof. Peter Beak for suggesting ion-pair phenomena as a mechanistic explanation for these results.
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48. Corey, E. J.; Kania, R. S. J. Am. Chem. Soc. 1996, 118, 1229.
49. See the Supporting Information for details on chemical degradation and NOESY experiments resulting in the structural assignment for compound 19.