Unique Strategy for the Assembly of the Carbon Skeleton of Guanacastepene a Using an Allenic Pauson - Khand-Type Reaction

Organic Letters

Volumn 5, Issue 19, 2003, Pages 3491-3494

  Brummond, Kay M ^a   Gao, Dong ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANTIBIOTIC AGENT; CARBON; GUANACASTEPENE A; RHODIUM; UNCLASSIFIED DRUG;

ALLENIC PAUSON KHAND REACTION; ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; DRUG STRUCTURE; NUCLEAR MAGNETIC RESONANCE; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

ANTI-BACTERIAL AGENTS; CYCLIZATION; CYCLOHEXANONES; DITERPENES; DRUG DESIGN; MOLECULAR STRUCTURE; RUTHENIUM;

EID: 0344824443     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol035322x     Document Type: Article

References (39)

1. Gonzales, R. D.; Schreckenberger, P. C.; Graham, M. B.; Kelkar, S.; DenBesten, K.; Quinn, J. P. Lancet 2001, 357, 1179.
2. Brady, S. F.; Singh, M. P.; Janso, J. E.; Clardy, J. J. Am. Chem. Soc. 2000, 122, 2116.
3. Brady, S. F.; Bondi, S. M.; Clardy, J. J. Am. Chem. Soc. 2001, 123, 9900.
4. Singh, M. P.; Janso, J. E.; Luckman, S. W.; Brady, S. F.; Clardy, J.; Greenstein, M.; Maiese, W. M. J. Antibiot. 2000, 53, 256.
5. (a) Dudley, G. B.; Danishefsky, S. J. Org. Lett. 2001, 3, 2399.
6. (b) Dudley, G. B.; Tan, D. S.; Kim, G.; Tanski, J. M.; Danishefsky, S. J. Tetrahedron Lett. 2001, 42, 6789.
7. (c) Magnus, P.; Waring, M. J.; Ollivier, C.; Lynch, V. Tetrahedron Lett. 2001, 42, 4947.
8. (d) Snider, B. B.; Shi, B. Tetrahedron Lett. 2001, 42, 9123.
9. (e) Snider, B. B.; Hawryluk, N. A. Org. Lett. 2001, 3, 569.
10. (f) Dudley, G. B.; Danishefsky, S. J.; Sukenick, G. Tetrahedron Lett. 2002, 43, 5605; Mehta, G.; Umarye, J. D. Org. Lett. 2002, 4, 1063.
11. (f) Dudley, G. B.; Danishefsky, S. J.; Sukenick, G. Tetrahedron Lett. 2002, 43, 5605; Mehta, G.; Umarye, J. D. Org. Lett. 2002, 4, 1063.
12. (g) Mehta, G.; Umarye, J. D.; Gagliardini, V. Tetrahedron Lett. 2002, 43, 6975.
13. (h) Shipe, W. D.; Sorensen, E. J. Org. Lett. 2002, 4, 2063.
14. (i) Nguyen, T. M.; Lee, D. Tetrahedron Lett. 2002, 43, 4033.
15. (j) Nguyen, T. M.; Seifert, R. J.; Mowrey, D. R.; Lee, D. Org. Lett. 2002, 4, 3959.
16. (k) Nakazaki, A.; Sharma, U.; Tius, M. A. Org. Lett. 2002, 4, 3363.
17. (l) Boyer, F. D.; Hanna, I. Tetrahedron Lett. 2002, 43, 7469.
18. (m) Tan, D. S.; Dudley, G. B.; Danishefsky, S. J. Angew. Chem., Int. Ed. 2002, 41, 2185.
19. (n) Lin, S.; Dudley, G. B.; Tan, D. S.; Danishefsky, S. J. Angew. Chem., Int. Ed. 2002, 41, 2188.
20. (o) Shi, B.; Hawryluk, N. A.; Snider, B. B. J. Org. Chem. 2003, 68, 1030.
21. (p) Mehta, G.; Umarye, J. D.; Srinivas, K. Tetrahedron Lett. 2003, 44, 4233.
22. (q) Xiaohui, D.; Chu, H. V.; Kwon, O. Org. Lett. 2003, 5, 1923.
23. Brummond, K. M.; Chen, H.; Fisher, K. D.; Kerekes, A. D.; Rickards, B.; Sill, P. C.; Geib, S. J. Org. Lett. 2002, 11, 1931. Narasaka published a similar result as a single example during our investigations into the scope of this reaction. Kobayashi, T. Koga, Y.; Narasaka, K. J. Organomet. Chem. 2001, 624, 73. Another group has reported the formation of bicyclo[5.3.0]-dec-1,7- dien-9-ones from allenes via rhodium(I) catalysis. Mukai, C.; Nomura, I.; Yamanishi, K.; Hanaoka, M. Org. Lett. 2002, 4, 1755.
24. Brummond, K. M.; Chen, H.; Fisher, K. D.; Kerekes, A. D.; Rickards, B.; Sill, P. C.; Geib, S. J. Org. Lett. 2002, 11, 1931. Narasaka published a similar result as a single example during our investigations into the scope of this reaction. Kobayashi, T. Koga, Y.; Narasaka, K. J. Organomet. Chem. 2001, 624, 73. Another group has reported the formation of bicyclo[5.3.0]-dec-1,7- dien-9-ones from allenes via rhodium(I) catalysis. Mukai, C.; Nomura, I.; Yamanishi, K.; Hanaoka, M. Org. Lett. 2002, 4, 1755.
25. Brummond, K. M.; Chen, H.; Fisher, K. D.; Kerekes, A. D.; Rickards, B.; Sill, P. C.; Geib, S. J. Org. Lett. 2002, 11, 1931. Narasaka published a similar result as a single example during our investigations into the scope of this reaction. Kobayashi, T. Koga, Y.; Narasaka, K. J. Organomet. Chem. 2001, 624, 73. Another group has reported the formation of bicyclo[5.3.0]-dec-1,7- dien-9-ones from allenes via rhodium(I) catalysis. Mukai, C.; Nomura, I.; Yamanishi, K.; Hanaoka, M. Org. Lett. 2002, 4, 1755.
26. Stork, G.; Danheiser, R. L. J. Org. Chem. 1973, 38, 1775.
27. Smith, A. B., III; Dorsey, B. D.; Ohba, M.; Lupo, A. T., Jr.; Malamas, M. S. J. Org. Chem. 1988, 53, 4314.
28. Alkyl iodide 8 was prepared in three steps from 3-methyl-1-butyne (see Supporting Information). Deprotonation of 3-methyl-1-butyne with n-BuLi followed by the addition of ethylene oxide gives the homopropargylic alcohol 9 in 95% yield. Conversion of this alcohol to the iodide was done using a standard protocol whereby the mesylate 10 was prepared using triethylamine and methanesulfonyl chloride. The mesylate 10 was not purified but taken directly onto 1-iodo-5-methyl-3-butyne (8) by refluxing in acetone and sodium iodide.
29. Studies on the dialkylation of vinylogous esters have been performed, see: (a) Foote, K. M.; John, M.; Pattenden, G. Synlett 2001, 3, 365-368. (b) Schinzer, D.; Dettmer, G.; Ruppelt, M. J. Org. Chem. 1988, 53, 3823-3828.
30. Studies on the dialkylation of vinylogous esters have been performed, see: (a) Foote, K. M.; John, M.; Pattenden, G. Synlett 2001, 3, 365-368. (b) Schinzer, D.; Dettmer, G.; Ruppelt, M. J. Org. Chem. 1988, 53, 3823-3828.
31. Diastereomers were separated by HPLC for characterization purposes. (see Supporting Information)
32. Fleming, I.; Terrett, N. K. J. Organomet. Chem. 1984, 264, 99. See also: Weinreb, S. M.; Jin, J. J. Am. Chem. Soc. 1997, 119, 5773.
33. Fleming, I.; Terrett, N. K. J. Organomet. Chem. 1984, 264, 99. See also: Weinreb, S. M.; Jin, J. J. Am. Chem. Soc. 1997, 119, 5773.
34. Studies performed previously in our group have shown that Pauson-Khand reactions can be sterically directed to react with one double bond selectively. Thus, introduction of the silicon group at the proximal double bond of the allene followed by its removal at an opportune time in the synthesis seemed to be advantageous. Brummond, K. M.; Lu, J. J. Am. Chem. Soc. 1999, 121, 5087. Moreover, this additional control element may not be necessary since the Pauson-Khand ring closure of 18 (R = H) with the proximal double bond would encounter a serious interaction between the newly formed exocyclic double bond and the hydroxymethyl group on the six-membered ring.
35. For a review, see: Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. For a mechanistic discussion, see: Vellekoop, A. S.; Smith, R. A. J. Am. Chem. Soc. 1994, 116, 2902.
36. For a review, see: Lipshutz, B. H.; Sengupta, S. Org. React. 1992, 41, 135. For a mechanistic discussion, see: Vellekoop, A. S.; Smith, R. A. J. Am. Chem. Soc. 1994, 116, 2902.
37. Horiguchi, Y.; Matsuzawa, S.; Nakamura, E.; Kuwajima, I. Tetrahedron Lett. 1986, 34, 4025. Nakamura, E.; Matsuzawa, S.; Horiguchi, Y.; Kumwajima, I. Tetrahedron Lett. 1986, 34, 4029.
38. Horiguchi, Y.; Matsuzawa, S.; Nakamura, E.; Kuwajima, I. Tetrahedron Lett. 1986, 34, 4025. Nakamura, E.; Matsuzawa, S.; Horiguchi, Y.; Kumwajima, I. Tetrahedron Lett. 1986, 34, 4029.
39. Methyl and tert-butyldimethylsilyl ethers were used in two independent calculations. Conformational analysis gave similar results, so the methyl ether depiction was used for viewing ease.