Enantioselective Pictet-Spengler-type cyclizations of hydroxylactams: H-bond donor catalysis by anion binding

Journal of the American Chemical Society

Volumn 129, Issue 44, 2007, Pages 13404-13405

  Raheem, Izzat T ^a   Thiara, Parvinder S ^a   Peterson, Emily A ^a   Jacobsen, Eric N ^a  

^a HARVARD UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ANION; HYDROXYLACTAM DERIVATIVE; LACTAM DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL BINDING; CHIRALITY; CYCLIZATION; ENANTIOSELECTIVITY; HYDROGEN BOND; PICTET SPENGLER REACTION; PROTON NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; SYNTHESIS;

ANIONS; BINDING SITES; CATALYSIS; CYCLIZATION; HYDROGEN BONDING; LACTAMS; MOLECULAR STRUCTURE; STEREOISOMERISM;

EID: 35948942795     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja076179w     Document Type: Article

References (34)

1. For reviews see: (a) Maryanoff, B. E.; Zhang, H.-C.; Cohen, J. H.; Turchi, I. J.; Maryanoff, C. A. Chem. Rev. 2004, 104, 1431-1628.
2. (b) Royer, J.; Bonin, M.; Micouin, L. Chem. Rev. 2004, 104, 2311-2352.
3. (c) Cox, E. D.; Cook, J. M. Chem. Rev. 1995, 95, 1797-1842.
4. (d) Speckamp, W. N.; Hiemstra, H. Tetrahedron 1985, 41, 4367-4416.
5. (a) Takamura, M.; Funabashi, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2000, 122, 6327-6328.
6. (b) Takamura, M.; Funabashi, K.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 6801-6802.
7. (c) Funabashi, K.; Ratni, H.; Kanai, M.; Shibasaki, M. J. Am. Chem. Soc. 2001, 123, 10784-10785.
8. (a) Taylor, M. S.; Jacobsen, E. N. J. Am. Chem. Soc. 2004, 126, 10558-10559.
9. (b) Taylor, M. S.; Tokunaga, N.; Jacobsen, E. N. Angew. Chem., Int. Ed. 2005, 44, 6700-6704.
10. (a) Pan, S. C.; Zhou, J.; List, B. Angew. Chem., Int. Ed. 2007, 46, 612-615.
11. (b) Pan, S. C.; List, B. Org. Lett. 2007, 9, 1149-1151.
12. (a) Hubert, J. C.; Speckamp, W. N.; Huisman, H. O. Tetrahedron Lett. 1972, 13, 4493-4496.
13. (b) Hubert, J. C.; Wijnberg, J. B. P. A.; Speckamp, W. N. Tetrahedron 1975, 31, 1437-1441.
14. See Supporting Information for further details.
15. Kam, T.-S.; Sim, K.-M. Phytochemistry 1998, 47, 145-147.
16. For alternative synthetic approaches to harmicine, see: Szawkało, J.; Czarnocki, S. J.; Zawadzka, A.; Wojtasiewicz, K.; Leniewski, A.; Maurin, J. K.; Czarnockia, Z.; Drabowicz, J. Tetrahedron: Asymmetry 2007, 18, 406-413 and references cited therein.
17. (a) Bose, A. K.; Spiegelman, G.; Manhas, M. S. Tetrahedron Lett. 1971, 3167.
18. (b) Nortey, S. O.; McComsey, D. F.; Maryanoff, B. E. Heterocycles 1993, 35, 1075-1088.
19. (a) Bailey, P. D. J. Chem. Res. 1987, 202-203.
20. (b) Czerwiński, K. M.; Deng, L.; Cook, J. M. Tetrahedron Lett. 1992, 33, 4721-4724.
21. (c) Bailey, P. D.; Hillinshead, S. P.; McLay, N. R.; Morgan, K.; Palmer, S. J.; Prince, S. N.; Reynolds, C. D.; Wood, S. D. J. Chem. Soc., Perkin Trans. 1 1993, 431-439.
22. (d) Kowalski, P.; Bojarski, A. J.; Mokrosz, J. L. Tetrahedron 1995, 51, 2737-2742.
23. No KIE was observed in reactions in which the indole C2 position of 3a was deuterated, ruling out the possibility of rate-limiting deprotonation/ rearomatization step from 4d.
24. DFT calculations of fully ionized N-acyliminium ions interacting with thiourea derivatives failed to converge on any ground state bound structure. See Supporting Information.
25. Similar reactivity and slightly diminished enantioselectivities are observed in reactions of urea analogues of catalyst 1 (e.g., 90% ee with 1a, and 75% ee with the urea analogue) in the cyclization of 3a. This appears to rule out a direct, productive interaction of the urea thiocarbonyl with the N-acyliminium ion.
26. This effect may be ascribed to several factors, including a trend toward poorer ion pairing, weaker binding to the thiourea, or increased background reactivity with the increase and size and leaving group ability of the halide.
27. (a) Schmidtchen, F. P.; Berger, M. Chem. Rev. 1997, 97, 1609-1646.
28. (b) Antonisse, M. M. G.; Reinhoudt, D. N. Chem. Commun. 1998, 443-448.
29. (c) Hisaki, I.; Sasaki, S.-I.; Hirose, K.; Tobe, Y. Eur. J. Org. Chem. 2007, 607-615.
30. (d) Jagessar, R. C.; Shang, M.; Scheidt, W. R.; Burns, D. H. J. Am. Chem. Soc. 1998, 120, 11684-11692.
31. 1H NMR spectra of equimolar solutions of 1b and tetrabutylammonium chloride revealed direct evidence for chloride binding to the thiourea. See Supporting Information.
32. Maruoka, K.; Ooi, T. Chem. Rev. 2003, 103, 3013-3028 and references therein.
33. (a) Mayer, S.; List, B. Angew. Chem., Int. Ed. 2006, 45, 4193-4195.
34. (b) Hamilton, G. L.; Rang, E. J.; Mba, M.; Toste, F. D. Science 2007, 317, 496-499.