Total synthesis of (-)-strychnine via the Wieland - Gumlich aldehyde

Angewandte Chemie - International Edition

Volumn 38, Issue 3, 1999, Pages 395-397

  Solé, Daniel ^a   Bonjoch, Josep ^a   García Rubio, Silvina ^a   Peidró, Emma ^a   Bosch, Joan ^a  

^a UNIVERSITY OF BARCELONA   (Spain)

Author keywords

Alkaloids; Asymmetric synthesis; Nitrogen heterocycles; Palladium; Total synthesis

Indexed keywords

ALDEHYDE; ALKALOID; HETEROCYCLIC COMPOUND; NITROGEN DERIVATIVE; PALLADIUM; STRYCHNINE;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHIRALITY; CYCLIZATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STOICHIOMETRY; SYNTHESIS; THIN LAYER CHROMATOGRAPHY;

EID: 0033082707     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1521-3773(19990201)38:3<395::AID-ANIE395>3.0.CO;2-5     Document Type: Article

References (34)

1. a) U. Beifuss, Angew. Chem. 1994, 106, 1204-1209; Angew. Chem. Int. Ed. Engl. 1994, 33, 1144-1149;
2. a) U. Beifuss, Angew. Chem. 1994, 106, 1204-1209; Angew. Chem. Int. Ed. Engl. 1994, 33, 1144-1149;
3. b) "Monoterpenoid Indole Alkaloids": J. Sapi, G. Massiot in The Chemistry of Heterocyclic Compounds, Suppl. to Vol. 25, Part 4 (Eds.: J. E. Saxton, E. C. Taylor), Wiley, New York, 1994, pp. 279-355;
4. c) J. Bosch, J. Bonjoch, M. Amat in The Alkaloids, Vol. 48 (Ed.: G. A. Cordell), Academic Press, New York, 1996, pp. 75-189;
5. d) K. C. Nicolaou, E. J. Sorensen, Classics in Total Synthesis, VHC. Weinheim, 1996, pp. 21-40, 641-653.
6. Moreover, it remains to be of interest from a pharmacological point of view; see, for example, P. Gharagozloo, M. Miyauchi, B. Birdsall, N. J. M. Birdsall, J. Org. Chem. 1998, 63, 1974-1980, and references therein.
7. R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger, H. U. Daeniker, K. Schenker, J. Am. Chem. Soc. 1954, 76, 4749-4751; R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger. H. U. Daeniker, K. Schenker, Tetrahedron 1963, 19, 247-288.
8. R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger, H. U. Daeniker, K. Schenker, J. Am. Chem. Soc. 1954, 76, 4749-4751; R. B. Woodward, M. P. Cava, W. D. Ollis, A. Hunger. H. U. Daeniker, K. Schenker, Tetrahedron 1963, 19, 247-288.
9. a) M. E. Kuehne, F. Xu, J. Org. Chem. 1993, 58, 7490-7497;
10. b) V. H. Rawal, S. Iwasa, J. Org. Chem. 1994, 59, 2685-2686; see also reference [3].
11. a) P. Magnus, M. Giles, R. Bonnert, C. S. Kim, L. McQuire, A. Merritt, N. Vicker, J. Am. Chem. Soc. 1992, 114, 4403-4405; P. Magnus, M. Giles, R. Bonnert, G. Johnson, L. McQuire, M. Deluca, A. Merritt, C. S. Kim, N. Vicker, J. Am. Chem. Soc. 1993, 115, 8116-8129;
12. a) P. Magnus, M. Giles, R. Bonnert, C. S. Kim, L. McQuire, A. Merritt, N. Vicker, J. Am. Chem. Soc. 1992, 114, 4403-4405; P. Magnus, M. Giles, R. Bonnert, G. Johnson, L. McQuire, M. Deluca, A. Merritt, C. S. Kim, N. Vicker, J. Am. Chem. Soc. 1993, 115, 8116-8129;
13. b) G. Stork, reported at the Ischia Advanced School of Organic Chemistry, Ischia Porto, Italy. 1992;
14. c) S. D. Knight, L. E. Overman, G. Pairaudeau, J. Am. Chem. Soc. 1993, 115, 9293-9294; S. D. Knight, L. E. Overman, G. Pairaudeau, J. Am. Chem. Soc. 1995, 117, 5776- 5788.
15. c) S. D. Knight, L. E. Overman, G. Pairaudeau, J. Am. Chem. Soc. 1993, 115, 9293-9294; S. D. Knight, L. E. Overman, G. Pairaudeau, J. Am. Chem. Soc. 1995, 117, 5776-5788.
16. a) M. Amat, A. Linares, J. Bosch, J. Org. Chem. 1990, 55, 6299-6312;
17. b) J. Gràcia, N. Casamitjana, J. Bonjoch, J. Bosch, J. Org. Chem. 1994, 59, 3939-3951;
18. c) M. Amat, M.-D. Coll, J. Bosch, E. Espinosa, E. Molins, Tetrahedron: Asymmetry 1997, 8, 935-948;
19. d) J. Bonjoch, D. Solé, S. García-Rubio, J. Bosch, J. Am. Chem. Soc. 1997, 119, 7230-7240.
20. The numbering system and ring labeling used throughout this paper is based on the biogenetic interrelationship of indole alkaloids: J. Le Men, W. I. Taylor, Experientia 1965, 21, 508-510.
21. In a preliminary study, this amine proved to be the most efficient chiral auxiliary for the enantioselective preparation of cis-3a-(2-nitrophenyl)octahydroindol-4-ones: D. Solé, J. Bosch, J. Bonjoch, Tetrahedron 1996, 52, 4013-4028.
22. [4b]
23. It was expected that the transient alkylpalladium intermediate arising from the cyclization, which has no β-hydrogen atom available for β-elimination, was stable enough to allow intermolecular trapping with CO; for related processes, see R. Grigg, P. Kennewell, A. Teasdale, Tetrahedron Lett. 1992, 33, 7789-7792; E. Negishi, C. Coperet, S. Ma. T. Mita, T. Sugihara, J. M. Tour, J. Am. Chem. Soc. 1996, 118, 5904- 5918.
24. It was expected that the transient alkylpalladium intermediate arising from the cyclization, which has no β-hydrogen atom available for β- elimination, was stable enough to allow intermolecular trapping with CO; for related processes, see R. Grigg, P. Kennewell, A. Teasdale, Tetrahedron Lett. 1992, 33, 7789-7792; E. Negishi, C. Coperet, S. Ma. T. Mita, T. Sugihara, J. M. Tour, J. Am. Chem. Soc. 1996, 118, 5904-5918.
25. 2O) under a variety of experimental conditions.
26. [12b] the azatricyclic compound 5 was the only isolable compound (<%);
27. b) R. Grigg, V. Santhakumar, V. Sridharan, Tetrahedron Lett. 1993, 34, 3163-3164.
28. a) In the Heck reaction with electron-deficient olefins, two competing reaction pathways can operate, namely, substitution (which involves β-H elimination) and 1.4-conjugate addition (which involves reduction of the σ-alkylpalladium intermediate); see, for example, G. K. Friestad, B. P. Branchaud, Tetrahedron Lett. 1997, 38, 5933-5936; H. Hagiwara, Y. Eda, K. Morohashi, T. Suzuki, M. Ando, N. Ito, Tetrahedron Lett. 1998, 39, 4055-4058, and references therein;
29. a) In the Heck reaction with electron-deficient olefins, two competing reaction pathways can operate, namely, substitution (which involves β- H elimination) and 1.4-conjugate addition (which involves reduction of the σ-alkylpalladium intermediate); see, for example, G. K. Friestad, B. P. Branchaud, Tetrahedron Lett. 1997, 38, 5933-5936; H. Hagiwara, Y. Eda, K. Morohashi, T. Suzuki, M. Ando, N. Ito, Tetrahedron Lett. 1998, 39, 4055-4058, and references therein;
30. [4b] involves a nonreductive intramolecular Heck reaction from a tetracyclic ABCE intermediate.
31. The chemical shifts of our synthetic sample were coincident with those reported for a natural sample of the Wieland-Gumlich aldehyde: G. Massiot, B. Massoussa, M.-J. Jacquier, P. Thépénier, L. Le Men-Olivier, C. Delaude, R. Verpoorte, Phytochemistry 1988, 27, 3293-3304.
32. [6d] we have also completed the synthesis of the racemic Wieland-Gumlich aldehyde.
33. F. A. L. Anet, R. Robinson, Chem. Ind. (London) 1953, 245.
34. This ee value is in agreement with the optical purity of 2, which was prepared from an (S)-1-phenylethylamine with about 96 % ee and used as a 97:3 mixture (according to HPLC analysis) of cis diastereomers.