Conversion of δ-(sulfonyl)amino-α-epoxy ketones to bicyclic ketopyrroles via intramolecular conjugate-addition to azoene intermediates. Synthesis of the bicyclic ketopyrrole core of the 1-azafulvene roseophilin

Tetrahedron Letters

Volumn 37, Issue 15, 1996, Pages 2545-2548

  Kim, Seong Heon ^a   Fuchs, P L ^a  

^a PURDUE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CYTOTOXIC AGENT; PYRROLE DERIVATIVE; ROSEOPHYLLIN; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; REACTION ANALYSIS;

EID: 0029931939     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00390-5     Document Type: Article

References (25)

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4. (a) Flaugh, M. E.; Rapoport, H. J. Am. Chem. Soc. 1968, 90, 6877;
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11. 4) failed to afford 13a.
12. Molecular modeling results using CAChe v. 3.7.
13. An alternative mechanism for production of 17a would be via formation of 13a followed by Shapiro reaction (see: Chamberlin, A. R.; Bloom, S. H. Organic Reactions, 1990, 39, 1, John Wiley, New York) of the p-tosylhydrazone moiety. Evidence which argues against such a possibility is the observation that the p-tosylhydrazone of 13b generates a plethora of products when subjected to NaH/DMF/100 °C. In marked contrast, the trisylhydrazone of 15b gives a 42% yield of the corresponding bicyclo [4.3.0] olefin which is stable to the reaction conditions above. For leading references to trisylhydrazone chemistry see: Nicolaou, K. C.; Yang, Z.; Sorensen, E. J.; Nakada, M. J. Chem. Soc. Chem. Commun. 1993, 1024.
14. An alternative mechanism for production of 17a would be via formation of 13a followed by Shapiro reaction (see: Chamberlin, A. R.; Bloom, S. H. Organic Reactions, 1990, 39, 1, John Wiley, New York) of the p-tosylhydrazone moiety. Evidence which argues against such a possibility is the observation that the p-tosylhydrazone of 13b generates a plethora of products when subjected to NaH/DMF/100 °C. In marked contrast, the trisylhydrazone of 15b gives a 42% yield of the corresponding bicyclo [4.3.0] olefin which is stable to the reaction conditions above. For leading references to trisylhydrazone chemistry see: Nicolaou, K. C.; Yang, Z.; Sorensen, E. J.; Nakada, M. J. Chem. Soc. Chem. Commun. 1993, 1024.
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17. 3 during which time it underwent cyclization to 14a.
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21. For NBS or DDQ oxidation of pyrrolines, see Shim, Y. K., et al. Synthesis 1990, 753; NBS oxidation of 21a,b gave some brominated compound along with the pyrroles. DDQ oxidation gave 22a,b in only moderate yield (∼60%).
22. Evans, D. A.; Faul, M. T; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742;. Knight. J. G.; Muldowney, M. P. Synlett 1995, 949; Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889.
23. Evans, D. A.; Faul, M. T; Bilodeau, M. T. J. Am. Chem. Soc. 1994, 116, 2742;. Knight. J. G.; Muldowney, M. P. Synlett 1995, 949; Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889.
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25. Craig has shown that substituted sulfonyl aziridines react with α-sulfonyl anions at the least substituted carbon (Berry, M. B.; Craig, D.; Jones, P. S. Synlett 1993, 513).