Enantioselective construction of vicinal stereogenic quaternary centers by dialkylation: Practical total syntheses of (+)- and meso-chimonanthine

Angewandte Chemie - International Edition

Volumn 39, Issue 1, 2000, Pages 213-215

  Overman, Larry E ^a   Larrow, Jay F ^a   Stearns, Brian A ^a   Vance, Jennifer M ^a  

^a UNIVERSITY OF CALIFORNIA   (United States)

Author keywords

Alkaloids; Alkylations; Asymmetric synthesis; Total synthesis

Indexed keywords

CHIMONANTHINE; INDOLE ALKALOID; UNCLASSIFIED DRUG;

ARTICLE; CHEMICAL STRUCTURE; ENANTIOMER; FROG; PLANT; STEREOCHEMISTRY; SYNTHESIS;

EID: 0034598476     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(20000103)39:1<213::AID-ANIE213>3.0.CO;2-Z     Document Type: Article

References (24)

1. Recent reviews of asymmetric synthesis of quaternary centers; a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401;
2. Recent reviews of asymmetric synthesis of quaternary centers; a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401;
3. b) K. Fuji, Chem. Rev. 1993, 93, 2037-2066.
4. For an excellent recent strategy, see R. M. Lemieux, A. I. Meyers, J. Am. Chem. Soc. 1998, 120, 5453-5457.
5. Y. Adjibadé, B. Weniger, J. C. Quirion, B. Kuballa, P. Cabalion, R. Anton, Phytochemistry 1992, 31, 317-319.
6. H. F. Hodson, B. Robinson, G. F. Smith, Proc. Chem. Soc. London 1961, 465-466.
7. T. Tokuyama, J. W. Daly, Tetrahedron 1983, 39, 41-47.
8. L. Verotta, T. Pilati, M. Tatò, E. Elisabetsky, T. A. Amador, D. S. Nunes, J. Nat. Prod. 1998, 61, 392-396.
9. R. K. Duke, R. D. Allan, G. A. R. Johnston, K. N. Mewett, A. D. Mitrovic, C. C. Duke, T. W. Hambley, J. Natl. Prod. 1995, 58, 1200-1208.
10. F. Guéritte-Voegelein, T. Sévenet, J. Pusset, M.-T. Adeline, B. Gillet, J.-C. Beloeil, D. Guénard, P. Potier, R. Rasolonjanahary, C. Kordon, J. Nat. Prod. 1992, 55, 923-930.
11. E. S. Hall, F. McCapra, A. I. Scott, Tetrahedron 1967, 23, 4131-4141.
12. a) R. Göschke, J. B. Hendrickson, R. Rees, Tetrahedron 1964, 20, 565-579;
13. b) C. L. Fang, S. Horne, N. Taylor, R. Rodrigo, J. Am. Chem. Soc. 1994, 116, 9480-9486.
14. T. Hino, S. Yamada, Tetrahedron Lett. 1963, 1757-1760.
15. J. T. Link, L. E. Overman, J. Am. Chem. Soc. 1996, 118, 8166-8167.
16. L. E. Overman, D. V. Paone, B. A. Stearns, J. Am. Chem. Soc. 1999, 121, 7702-7703.
17. 2O at 0 C. Both enantiomers of this intermediate are available from (+)-and ( )-tartaric acid: E. A. Mash, K. A. Nelson, S. Van Deusen, S. B. Hemperly in Organic Syntheses, Vol. 68 (Ed.: J. D. White), Wiley, New York, 1990, pp. 92-103.
18. [11]
19. Consistent with this interpretation, stereoselection was eroded in the presence of a sodium-selective cryptand (Kryptofix 221).
20. R. M. Williams, E. Kwast, Tetrahedron Lett. 1989, 30, 451-454.
21. Crystallographic data (excluding structure factors) for the structure reported in this paper have been deposited with the Cambridge Cristallographic Data Centre as supplementary publication no. CCDC-134670. Copies of the data can be obtained free of charge on application to CCDC, 12 Union Road. Cambridge CB2 1EZ, UK (fax: (+44) 1223-336-033; e-mail: deposit@ccdc.cam.ac.uk).
22. D - + 264.5 (c 1.0 in EtOH).
23. a) A recent survey of stereoselective C - C bond formation cites no examples in sections dealing with alkylation reactions with chiral electrophiles; see D. S. Matteson, Methoden Org. Chem. (Houben-Weyl) 4th ed. 1996, Vol. E21/2, pp. 1077-1118;
24. b) Interconversion of atropisomers of the dienolates derived from 6 is likely to be slow under the alkylation conditions. Whether the 20:1 selectivity arises solely in the initial alkylation step or is enhanced by selective partitioning of the minor diastereomer in the cyclization step has not yet been determined.