Catalytic enantioselective synthesis of oxindoles and benzofuranones that bear a quaternary stereocenter

Angewandte Chemie - International Edition

Volumn 42, Issue 33, 2003, Pages 3921-3924

  Hills, Ivory D ^a   Fu, Gregory C ^a  

^a MASSACHUSETTS INSTITUTE OF TECHNOLOGY   (United States)

Author keywords

Asymmetric synthesis; Heterocycles; Homogeneous catalysis; Ion pairs; Rearrangements

Indexed keywords

CATALYSIS; SYNTHESIS (CHEMICAL);

HETEROCYCLE;

FURAN RESINS;

ANTINEOPLASTIC AGENT; BENZOFURAN DERIVATIVE; BENZOFURANONE; DIAZONAMIDE A; GELSEMINE; HETEROCYCLIC COMPOUND; INDOLE ALKALOID; NATURAL PRODUCT; OXINDOLE; UNCLASSIFIED DRUG;

ARTICLE; ASYMMETRIC SYNTHESIS; CATALYSIS; CHEMICAL STRUCTURE; CHIRALITY; CRYSTAL STRUCTURE; ENANTIOSELECTIVITY; SYNTHESIS; X RAY CRYSTALLOGRAPHY;

EID: 0042819678     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351666     Document Type: Article

References (40)

1. For a sampling of recent total syntheses, see: a) gelsemine: H. Lin, S. J. Danishefsky, Angew. Chem. 2003, 115, 38-53; Angew. Chem. Int. Ed. 2003, 42, 36-51; b) strychnofoline: A. Lerchner, E. M. Carreira, J. Am. Chem. Soc. 2002, 124, 14826-14827; c) alantrypinone: D. J. Hart, N. A. Magomedov, J. Am. Chem. Soc. 2001, 123, 5892-5899; d) spirotryprostatin B: L. E. Overman, M. D. Rosen, Angew. Chem. 2000, 112, 4768-4771; Angew. Chem. Int. Ed. 2000, 39, 4596-4599.
2. For a sampling of recent total syntheses, see: a) gelsemine: H. Lin, S. J. Danishefsky, Angew. Chem. 2003, 115, 38-53; Angew. Chem. Int. Ed. 2003, 42, 36-51; b) strychnofoline: A. Lerchner, E. M. Carreira, J. Am. Chem. Soc. 2002, 124, 14826-14827; c) alantrypinone: D. J. Hart, N. A. Magomedov, J. Am. Chem. Soc. 2001, 123, 5892-5899; d) spirotryprostatin B: L. E. Overman, M. D. Rosen, Angew. Chem. 2000, 112, 4768-4771; Angew. Chem. Int. Ed. 2000, 39, 4596-4599.
3. For a sampling of recent total syntheses, see: a) gelsemine: H. Lin, S. J. Danishefsky, Angew. Chem. 2003, 115, 38-53; Angew. Chem. Int. Ed. 2003, 42, 36-51; b) strychnofoline: A. Lerchner, E. M. Carreira, J. Am. Chem. Soc. 2002, 124, 14826-14827; c) alantrypinone: D. J. Hart, N. A. Magomedov, J. Am. Chem. Soc. 2001, 123, 5892-5899; d) spirotryprostatin B: L. E. Overman, M. D. Rosen, Angew. Chem. 2000, 112, 4768-4771; Angew. Chem. Int. Ed. 2000, 39, 4596-4599.
4. For a sampling of recent total syntheses, see: a) gelsemine: H. Lin, S. J. Danishefsky, Angew. Chem. 2003, 115, 38-53; Angew. Chem. Int. Ed. 2003, 42, 36-51; b) strychnofoline: A. Lerchner, E. M. Carreira, J. Am. Chem. Soc. 2002, 124, 14826-14827; c) alantrypinone: D. J. Hart, N. A. Magomedov, J. Am. Chem. Soc. 2001, 123, 5892-5899; d) spirotryprostatin B: L. E. Overman, M. D. Rosen, Angew. Chem. 2000, 112, 4768-4771; Angew. Chem. Int. Ed. 2000, 39, 4596-4599.
5. For a sampling of recent total syntheses, see: a) gelsemine: H. Lin, S. J. Danishefsky, Angew. Chem. 2003, 115, 38-53; Angew. Chem. Int. Ed. 2003, 42, 36-51; b) strychnofoline: A. Lerchner, E. M. Carreira, J. Am. Chem. Soc. 2002, 124, 14826-14827; c) alantrypinone: D. J. Hart, N. A. Magomedov, J. Am. Chem. Soc. 2001, 123, 5892-5899; d) spirotryprostatin B: L. E. Overman, M. D. Rosen, Angew. Chem. 2000, 112, 4768-4771; Angew. Chem. Int. Ed. 2000, 39, 4596-4599.
6. For a sampling of recent total syntheses, see: a) gelsemine: H. Lin, S. J. Danishefsky, Angew. Chem. 2003, 115, 38-53; Angew. Chem. Int. Ed. 2003, 42, 36-51; b) strychnofoline: A. Lerchner, E. M. Carreira, J. Am. Chem. Soc. 2002, 124, 14826-14827; c) alantrypinone: D. J. Hart, N. A. Magomedov, J. Am. Chem. Soc. 2001, 123, 5892-5899; d) spirotryprostatin B: L. E. Overman, M. D. Rosen, Angew. Chem. 2000, 112, 4768-4771; Angew. Chem. Int. Ed. 2000, 39, 4596-4599.
7. For a review of catalytic asymmetric methods that generate quaternary stereocenters, see: a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: b) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
8. For a review of catalytic asymmetric methods that generate quaternary stereocenters, see: a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: b) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
9. For a review of catalytic asymmetric methods that generate quaternary stereocenters, see: a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: b) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
10. For a review of catalytic asymmetric methods that generate quaternary stereocenters, see: a) E. J. Corey, A. Guzman-Perez, Angew. Chem. 1998, 110, 402-415; Angew. Chem. Int. Ed. 1998, 37, 388-401; see also: b) J. Christoffers, A. Mann, Angew. Chem. 2001, 113, 4725-4732; Angew. Chem. Int. Ed. 2001, 40, 4591-4597.
11. For example, the intramolecular asymmetric Heck reaction has proved to be useful; for leading references, see: a) A. D. Lebsack, J. T. Link, L. E. Overman, B.A. Stearns, J. Am. Chem. Soc. 2002, 124, 9008-9009; Y. Donde, L. E. Overman in Comprehensive Asymmetric Catalysis; (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, pp. 675-697.
12. For example, the intramolecular asymmetric Heck reaction has proved to be useful; for leading references, see: a) A. D. Lebsack, J. T. Link, L. E. Overman, B.A. Stearns, J. Am. Chem. Soc. 2002, 124, 9008-9009; Y. Donde, L. E. Overman in Comprehensive Asymmetric Catalysis; (Eds.: E. N. Jacobsen, A. Pfaltz, H. Yamamoto), Springer, New York, 1999, pp. 675-697.
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15. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
16. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
17. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
18. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
19. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
20. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
21. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
22. For the correct structural assignment of diazonamide A, see: a) J. Li, A. W. G. Burgett, L. Esser, C. Amezcua, P. G. Harran, Angew. Chem. 2001, 113, 4906-4909; Angew. Chem. Int. Ed. 2001, 40, 4770-4773; for an overview of diazonamide chemistry, see: b) T. Ritter, E. M. Carreira, Angew. Chem. 2002, 114, 2601-2606; Angew. Chem. Int. Ed. 2002, 41, 2489-2495; for the total synthesis of the corrected structure of diazonamide A, see: c) K. C. Nicolaou, M. Bella, D. Y.-K. Chen, X. Huang, T. Ling, S.A. Snyder, Angew. Chem. 2002, 114, 3645-3649; Angew. Chem. Int. Ed. 2002, 41, 3495-3499; K.C. Nicolaou, P. Bheema Rao, J. Hao, M. V. Reddy, G. Rassias, X. Huang, D. Y.-K. Chen, S. A. Snyder, Angew. Chem. 2003, 115, 1795-1800; Angew. Chem. Int. Ed. 2003, 42, 1753-1758.
23. C. J. Moody, K. J. Doyle, M. C. Elliott, T. J. Mowlem, J. Chem. Soc. Perkin Trans. 1 1997, 2413-2419.
24. E. Vedejs, J. Wang, Org. Lett. 2000, 2, 1031-1032.
25. For an early overview, see: a) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420; for intra- and intermolecular C-acylation reactions, see: b) J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 11532-11533; A. H. Mermerian, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 4050-4051; for additional applications, see: c) S. Arai, S. Bellemin-Laponnaz, G. C. Fu, Angew. Chem. 2001, 113, 240-242; Angew. Chem. Int. Ed. 2001, 40, 234-236; B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.2
26. For an early overview, see: a) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420; for intra- and intermolecular C-acylation reactions, see: b) J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 11532-11533; A. H. Mermerian, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 4050-4051; for additional applications, see: c) S. Arai, S. Bellemin-Laponnaz, G. C. Fu, Angew. Chem. 2001, 113, 240-242; Angew. Chem. Int. Ed. 2001, 40, 234-236; B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.2
27. For an early overview, see: a) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420; for intra- and intermolecular C-acylation reactions, see: b) J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 11532-11533; A. H. Mermerian, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 4050-4051; for additional applications, see: c) S. Arai, S. Bellemin-Laponnaz, G. C. Fu, Angew. Chem. 2001, 113, 240-242; Angew. Chem. Int. Ed. 2001, 40, 234-236; B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.2
28. For an early overview, see: a) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420; for intra- and intermolecular C-acylation reactions, see: b) J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 11532-11533; A. H. Mermerian, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 4050-4051; for additional applications, see: c) S. Arai, S. Bellemin-Laponnaz, G. C. Fu, Angew. Chem. 2001, 113, 240-242; Angew. Chem. Int. Ed. 2001, 40, 234-236; B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.2
29. For an early overview, see: a) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420; for intra- and intermolecular C-acylation reactions, see: b) J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 11532-11533; A. H. Mermerian, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 4050-4051; for additional applications, see: c) S. Arai, S. Bellemin-Laponnaz, G. C. Fu, Angew. Chem. 2001, 113, 240-242; Angew. Chem. Int. Ed. 2001, 40, 234-236; B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.2
30. For an early overview, see: a) G. C. Fu, Acc. Chem. Res. 2000, 33, 412-420; for intra- and intermolecular C-acylation reactions, see: b) J. C. Ruble, G. C. Fu, J. Am. Chem. Soc. 1998, 120, 11532-11533; A. H. Mermerian, G. C. Fu, J. Am. Chem. Soc. 2003, 125, 4050-4051; for additional applications, see: c) S. Arai, S. Bellemin-Laponnaz, G. C. Fu, Angew. Chem. 2001, 113, 240-242; Angew. Chem. Int. Ed. 2001, 40, 234-236; B. L. Hodous, G. C. Fu, J. Am. Chem. Soc. 2002, 124, 1578-1579.2
31. 2,2,2-Trichloro-1,1-dimethylethyl chloroformate is commercially available. The trichloro-tert-butoxycarbonyl group has been employed in kinetic resolutions of secondary alcohols by an N-acylated chiral derivative of DMAP: a) E. Vedejs, X. Chen, J. Am. Chem. Soc. 1996, 118, 1809-1810. Catalyst (-)-2 affords essentially identical enantioselectivity as (-)-1 (97% ee; same enantiomer of the product as (-)-1); we chose to focus our studies on catalyst 1, since it is particularly stable.
32. The absolute stereochemistry of the product of Table 2, entry 3 was determined by X-ray crystallography (see the Supporting Information); the other configurations were assigned by analogy.
33. 2 ([substrate] = 1.0M) was then added to the vial through a syringe, and the reaction mixture was heated at 35°C for 48 h. The reaction mixture was then applied directly to a silica-gel column for purification by flash chromatography (typically. -85% of the catalyst was recovered).
34. The slight difference in enantiomeric excess between Table 1, entry 4 and Table 2, entry 1 is due to the difference in the scale of the reactions. See the Supporting Information for additional details. [13] In preliminary studies, we selectively hydrolyzed (aqueous NaOH) and transesterified (NaOMe) the trichloro-tert-butyl ester group.
35. The absolute stereochemistry of the product of Table 3, entry 1 was determined by X-ray crystallography (see the Supporting Information); the other configurations were assigned by analogy.
36. We employed the product of Table 3, entry 3 in a formal total synthesis of debromoaplysin (I. D. Hills, unpublished results). (Equation Presentation)
37. Under our standard reaction conditions, the benzofuranone-derived substrates react more rapidly than do the oxindole-derived compounds.
38. In the original studies of Black et al., a solid was generated under certain conditions and speculated to be the ion-pair intermediate. Unfortunately, the solid could not be characterized.
39. The quality of the crystal was sufficiently high to unambiguously assign the structure of the ion pair, but not sufficiently high to accurately determine bond lengths. CCDC-208287 contains the supplementary crystallographic data for 3. These data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html (or from the Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB21EZ, UK; fax: (+44)1223-336-033; or deposit@ccdc.cam.ac.uk).
40. 1H NMR studies show that for the benzofuranone chemistry, the resting state of the catalyst is the N-acylated derivative, whereas for the oxindole chemistry, the resting state is the catalyst itself (not acylated).