Indole-2,3-quinodimethanes: A New Strategy for the Synthesis of Tetracyclic Systems of Indole Alkaloids

Journal of the American Chemical Society

Volumn 105, Issue 14, 1983, Pages 4739-4749

  Exon, Christopher ^a   Gallagher, Timothy ^a   Magnus, Philip ^a  

^a INDIANA UNIVERSITY   (United States)

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EID: 0020780726     PISSN: 00027863     EISSN: 15205126     Source Type: Journal    
DOI: 10.1021/ja00352a037     Document Type: Article

References (35)

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3. For leading references to attempts to carry out both inter- and intramolecular versions of the conversions of 1 into 2 and 3, both in the oxidation level depicted (dehydrosecodine) and the dihydro system (secodine), consult: (a) Kuehne, M. E.; Roland, D. M.; Hafter, R. J. Org. Chem. 1978, 43, 3703. Kuehne, M. E.; Matsko, T. H.; Bohnert, J. C.; Kirkemo, C. L. J. Org. Chem. 1979, 44, 1063. Kuehne, M. E.; Huebner, J. A.; Matsko, T. H. J. Org. Chem. 1979, 44, 2477. Kuehne, M. E.; Kirkemo, C. L.; Matsko, T. H.; Bohnert, J. C. J. Org. Chem. 1980, 45, 3259. Kuehne, M. E.; Matsko, T. H.; Bohnert, J. C.; Motyka, L.; Oliver-Smith, D. J. Org. Chem. 1981, 46, 2002. (b) Weinstein, B.; Chang Lin, L.; Fowler, F. W. J. Org. Chem. 1980, 45, 1657. (c) Kutney, J. P.; Badger, R. A.; Beck, J. F.; Bosshardt, H.; Matough, F. S.; Ridaura-Sanz, V. E.; So, Y. H.; Sood, R. S.; Worth, B. R. Can. J. Chem. 1979, 57, 289. Wilson, R. M.; Farr, R. A.; Burlett, D. J. J. Org. Chem. 1981, 46, 3293. Beeken, P.; Bonfiglio, J. N.; Hasan, H.; Piwinski, J. J.; Weinstein, B.; Zollo, K. A.; Fowler, F. W. J. Am. Chem. Soc. 1979, 101, 6677. (d) Secodine via Claisen rearrangement: Raucher, S.; Macdonald, J. E.; Lawrence, R. F. J. Am. Chem. Soc. 1981, 103, 2419. (e). Marazano, C.; Fourrey, J.-L.; Das, B. C. ]. Chem. Soc, Chem. Commun. 1977, 742; 1981, 37. Marazano, C.; LeGoff, M.-T.; Fourrey, J.-L.; Das, B. C. Chem. Soc, Chem. Commun. 1981, 389. Sundberg, R. J.; Bloom, J. D. J. Org. Chem. 1980, 45, 3382. Hasan, I.; Marinelli, E. R.; Chang Lin, L.-C; Fowler, F. W.; Levy, A. B. J. Org. Chem. 1981, 46, 157. (f) Büchi, G.; Coffen, D. L.; Koesis, K.; Sonnet, P. E.; Ziegler, F. E. J. Am. Chem. Soc. 1966, 88, 3099. (g) Ziegler, F. E.; Spitzner, E. B. J. Am. Chem. Soc. 1973, 95, 7146. Ziegler, F. E.; Bennett, G. B. J. Am. Chem. Soc. 1973, 95, 7458.
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7. Many other approaches have been developed. For a general review of indole alkaloid synthesis see: Kutney, J. P. In “The Total Synthesis of Natural Products”; ApSimon, J., Ed.; Wiley-Interscience: New York, 1977; Vol. 3, 273. Cordell, G. A. Alkaloids (N.Y.) 1979, 17, 200. (a) Oxindole approach: Ban, Y.; Ohnuma, T.; Nagai, M.; Sendo, Y.; Oishi, T. Tetrahedron Lett. 1972, 5023. Seki, K.; Ohnuma, T.; Oishi, T.; Ban, Y. Tetrahedron Lett. 1975, 723. Ohnuma, T.; Oishi, T.; Ban, Y. J. Chem. Soc, Chem. Commun. 1973, 301. (b) Nine-membered-ring intermediates: Kutney, J. P.; Brown, T. R.; Piers, E.; Hadfield, J. R. J. Am. Chem. Soc. 1970, 92, 1708. Kutney, J. P.; Cretney, W. J.; LeQuesne, P.; McKagne, B.; Piers, E. J. Am. Chem. Soc. 1970, 92, 1712. Kutney, J. P.; Chan, K. K.; Failli, A.; Fromson, J. M.; Gletsos, C.; Lentwiler, A.; Neilson, V. R.; de Souza, J. P. Helv. Chim. Acta 1975, 58, 1648. (c) Rearrangement route: Barton, J. E. D.; Harley-Mason, J. J. Chem. Soc, Chem. Commun. 1965, 298. Harley-Mason, J.; Kaplan, M. J. Chem. Soc, Chem. Commun. 1967, 915. (d) N-Acyliminium cyclization: Veenstra, S. J.; Speckamp, W. N. J. Am. Chem. Soc. 1981, 103, 4645. (e) Heteroatom-directed photoarylation: Schultz, A. G.; Chiu, I.-C. J. Chem. Soc, Chem. Commun. 1978, 29. (0 For other notable approaches see: Ando, M.; Büchi, G.; Ohnuma, T. J. Am. Chem. Soc. 1975, 97, 6880. Büchi, G.; Matsumoto, K. E.; Nishimura, H. J. Am. Chem. Soc. 1971, 93, 3299. Giri, V. S.; Ali, E.; Pakrashi, S. C. J. Heterocycl. Chem. 1980, 17, 1133. Laronze, J. Y.; Laronze-Fontaine, J.; Levy, J.; LeMen, J. Tetrahedron Lett. 1974, 491. Takano, S.; Shishido, K.; Matsuzaka, J.-L; Sato, M.; Ogasawara, K. Heterocycles 1979, 307.
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9. A detailed description of the experiments that led to the discovery of this reaction, along with some initial results, has already been published (Gallagher, T.; Magnus, P. Tetrahedron 1981, 37, 3889). Its extension to the total synthesis of dl-aspidospermidine: Gallagher, T.; Magnus, P. J. Am. Chem. Soc. 1982, 104, 1140; 1983, 105, accompanying paper.
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11. Oppolzer, W. J. Am. Chem. Soc. 1971, 93, 3833, 3834; Angew. Chem., Int. Ed. Engl. 1972, 1031; Tetrahedron Lett. 1974, 1001. For a comprehensive review of the intramolecular Diels-Alder reaction see: Brieger, G.; Bennett, J. N. Chem. Rev. 1980, 80, 63. For an extensive compilation of references to quinodimethanes (o-xylylenes) in synthesis see: Moder, K. P.; Leonard, N. J. J. Am. Chem. Soc. 1982, 104, 2613. Oppolzer, W. Synthesis 1978, 793. A number of N-acyl dienes have been used for the synthesis of alkaloids see: Oppolzer, W.; Bieber, L.; Franoctte Tetrahedron Lett. 1979, 981, 4537. Oppolzer, W.; Fröstl, W. Helv. Chim. Acta 1975, 58, 590. Oppolzer, W,; Frostl, W.; Weber, H. P. Helv. Chim. Acta 1975, 58, 593. Overman, L. E.; Taylor, G. F.; Jessup, P. J. Tetrahedron Lett. 1976, 3089. Overman, L. E.; Jessup, P. J. J. Am. Chem. Soc. 1978, 100, 5179. Overman, L. E.; Fukaya, C. J. Am. Chem. Soc. 1980, 102, 1454. Overman, L. E.; Petty, C. B.; Daedens, R. J. J. Org. Chem. 1979, 44, 4183.
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13. Dr. Peter Gund (merck) using the Merck Molecular Modeling System demonstrated that there is virtually no energy difference between 12 and 12a and that steric interactions twist the nitrogen atom of the dienamine out of conjugation with the diene system for both isomers. Interestingly, when applied to 11/11a for R = Me and X = NMe2, the structure 11a is favored by 0.6 kcal. Again in both 11 and 11a the nitrogen lone pair is orthogonal to the diene -system. As a note of caution, these particular calculations do not really apply to transition states and also have no Coulombic energy form in the ground-state classical mechanical energy calculations. Since this applies to both sets of compounds, the differences (or lack of) might be useful but should be regarded as tentative. Dr. Peter Gund is gratefully thanked for his time and interest in this matter.
14. Gallagher, T.; Magnus, P., unpublished results. See also: Exon, C.; Gallagher, T.; Magnus, P. J. Chem. Soc, Chem. Commun. 1982, 613.
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