Enantioselective total synthesis of the cyclotryptamine alkaloid idiospermuline

Angewandte Chemie - International Edition

Volumn 42, Issue 22, 2003, Pages 2525-2528

  Overman, Larry E ^a   Peterson, Emily A ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Alkaloids; Alkylation; Asymmetric catalysis; C C coupling; Heck reaction

Indexed keywords

CATALYSIS; LITHIUM COMPOUNDS; SYNTHESIS (CHEMICAL);

ELECTROPHILES;

ORGANIC COMPOUNDS;

ALKALOID DERIVATIVE; IDIOSPERMULINE; LITHIUM DERIVATIVE; TARTARIC ACID DERIVATIVE; TRYPTAMINE DERIVATIVE; UNCLASSIFIED DRUG;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; HECK REACTION; STRUCTURE ANALYSIS; SYNTHESIS;

ALKALOIDS; MOLECULAR STRUCTURE; PYRROLIDINONES; STEREOISOMERISM;

EID: 0037663859     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351260     Document Type: Article

References (28)

1. For a recent review, see: U. Anthoni, C. Christophersen, P. H. Nielsen, Alkaloids: Chemical and Biological Perspectives, Vol. 13 (Ed.: S. W. Pelletier), Pergamon, New York, 1999, pp. 163-236.
2. a) J. T. Link, L. E. Overman, J. Am. Chem. Soc. 1996, 118, 8166-8167;
3. b) L. E. Overman, D. V. Paone, B. A. Stearns, J. Am. Chem. Soc. 1999, 121, 7702-7703;
4. c) L. E. Overman, J. F. Larrow, B. A. Stearns, J. M. Vance, Angew. Chem. 2000, 112, 219-221; Angew. Chem. Int. Ed. 2000, 39, 213-215.
5. c) L. E. Overman, J. F. Larrow, B. A. Stearns, J. M. Vance, Angew. Chem. 2000, 112, 219-221; Angew. Chem. Int. Ed. 2000, 39, 213-215.
6. R. K. Duke, R. D. Allan, G. A. R. Johnston, K. N. Mewett, A. D. Mitrovic, C. C. Duke, T. W. Hambley, J. Nat. Prod. 1995, 58, 1200-1208.
7. a) M. Oestreich, P. R. Dennison, J. J. Kodanko, L. E. Overman, Angew. Chem. 2001, 113, 1485-1489; Angew. Chem. Int. Ed. 2001, 40, 1439-1442;
8. a) M. Oestreich, P. R. Dennison, J. J. Kodanko, L. E. Overman, Angew. Chem. 2001, 113, 1485-1489; Angew. Chem. Int. Ed. 2001, 40, 1439-1442;
9. b) A. B. Dounay, K. Hatanaka, J. J. Kodanko, M. Oestreich, L. E. Overman, L. A. Pfeifer, M. M. Weiss, J. Am. Chem. Soc. 2003, 125, in press (ASAP Web release April 23, 2003).
10. The utility of this transformation for attaching precursors of pyrrolidinoindoline fragments to a meso bis-3a,3 a′-bispyrrolidinoindoline moiety was demonstrated in our recent total synthesis of quadrigemine C, see: A. D. Lebsack, J. T. Link, L. E. Overman, B. A. Stearns, J. Am. Chem. Soc. 2002, 124, 9008-9009.
11. R. L. Autrey, F. C. Tahk, Tetrahedron 1967, 23, 901-917.
12. These studies were guided by our earlier systematic studies of the related condensation of 7 with the dibenzyl analogue of 8 en route to (-)-chimonanthine.
13. For a detailed study and analysis of a related dialkylation reaction, see S. B. Hoyt, L. E. Overman, Org. Lett. 2000, 2, 3241-3244.
14. The HMPA additive was necessary not only to reduce chelation during the intramolecular alkylation step, but also to solvate the substrate at low temperature.
15. See the Supporting Information for reagents and yields for each step in the elaboration of 10 to 11.
16. For examples of ortho-lithiation of N-(tert-butoxy)indolines see: a) M. Iwao, T. Kuraishi, Org. Synth. 1996, 73, 85-93; b) S. P. Govek, L. E. Overman, J. Am. Chem. Soc. 2001, 123, 9468-9469, and reference [5].
17. For examples of ortho-lithiation of N-(tert-butoxy)indolines see: a) M. Iwao, T. Kuraishi, Org. Synth. 1996, 73, 85-93; b) S. P. Govek, L. E. Overman, J. Am. Chem. Soc. 2001, 123, 9468-9469, and reference [5].
18. Stannyl butenanilide 13 is available in two steps from N-methylpropargylamine and 3-methylbenzoxazolinone, see the Supporting Information.
19. a) V. Farina, B. Krishnan, J. Am. Chem. Soc. 1991, 113, 9585-9595;
20. b) V. Farina, S. Kapadia, B. Krishnan, C. Wang, L. S. Liebeskind, J. Org. Chem. 1994, 59, 5905-5911;
21. c) L. S. Liebeskind, R. W. Fengl, J. Org. Chem. 1990, 55, 5359-5364.
22. (S)-Tol-BINAP = (S)-2,2′-bis(di-p-tolylphosphanyl)-1,1′-binaphthyl: H. Takaya, K. Mashima, K. Koyano, M. Yagi, H. Kumobayashi, T. Taketomi, S. Akutagawa, R. Noyori, J. Org. Chem. 1986, 51, 629-635.
23. 1H NMR (360K, for coalescence of rotamer signals) was used to determine the diastereomer ratio.
24. X.-F. Pei, S. Bi, Heterocycles 1994, 39, 357-360.
25. 3).
26. We thank Professor Rujee K. Duke for providing this sample.
27. J. J. Kodanko, L. E. Overman, Angew. Chem. 2003, 115, 2632-2635; Angew. Chem. Int. Ed. 2003, 42, 2528-2531 (following communication in this issue).
28. J. J. Kodanko, L. E. Overman, Angew. Chem. 2003, 115, 2632-2635; Angew. Chem. Int. Ed. 2003, 42, 2528-2531 (following communication in this issue).