Structural origins of a dramatic variation in catalyst efficiency in enantioselective alkene aziridination: Implications for design of ligands based on chiral biaryldiamines [10]

Journal of the American Chemical Society

Volumn 122, Issue 29, 2000, Pages 7132-7133

  Sanders, Christopher J ^a   Gillespie, Kevin M ^a   Bell, David ^b   Scott, Peter ^a  

^a UNIVERSITY OF WARWICK   (United Kingdom)

^b GLAXOSMITHKLINE   (United Kingdom)

Author keywords

[No Author keywords available]

Indexed keywords

ALKENE DERIVATIVE; AZIRIDINE DERIVATIVE; DIAMINE DERIVATIVE; LIGAND;

CATALYST; CHEMICAL STRUCTURE; CHIRALITY; CRYSTALLIZATION; ENANTIOMER; LETTER; LIGAND BINDING; REACTION ANALYSIS; STEREOCHEMISTRY;

EID: 0034718094     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja994353d     Document Type: Letter

References (28)

1. (a) Takaya, H.; Ohta, T.; Noyori, R. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: Weinheim, 1993.
2. (b) Noyori, R. Asymmetric Catalysis in Organic Synthesis; John Wiley and Sons: New York, 1994.
3. (a) Corey, E. J.; Imwikelreid, R.; Pikul, S.; Xiang Y. B. J. Am. Chem. Soc. 1989, 111, 5493.
4. (b) Chapuis, C.; Jurczak, Helv. Chim. Acta 1987, 70, 437.
5. (c) Narasaka, K. Synthesis 1991, 1, 1.
6. (d) Kagan, H. B.; Riant, O. Chem. Rev. 1992, 92, 1007.
7. (a) Gant, T. G.; Noe, M. C.; Corey, E. J. Tetrahedron Lett. 1995, 36, 8745.
8. (b) Uozomi, Y.; Kyota, H.; Kishi, E.; Kitayama, K.; Hayashi, T. Tetrahedron:Asymm. 1996, 8, 1603.
9. (c) Suga, H.; Fudo, T.; Ihata, T. Synlett 1998, 933.
10. Shi, M.; Itoh, N.; Masaki, Y. J. Chem. Res. M 1996, 1946.
11. (a) Evans, D. A.; Woerpel, K. A.; Hinman, M. M.; Faul, M. M. J. Am. Chem. Soc. 1991, 113, 726.
12. (b) Evans, D. A.; Faul, M. M.; Bilodeau, M. T. J. Org. Chem. 1991, 56, 6744.
13. (c) Evans, D. A.; Woerpel, K. A.; Scott, M. J. Angew. Chem., Int. Ed. Engl. 1992, 31, 430.
14. (d) Evans, D. A.; Faul, M. M.; Biodeau, M. T.; Anderson, B. J.; Barnes, D. M. J. Am. Chem. Soc 1993, 115, 5328.
15. (a) Li, Z.; Conser, K.; Jacobsen, E. N. J. Am. Chem. Soc. 1993, 115, 5326.
16. (b) Li, Z.; Quan, R. W.; Jacobsen, E. N. J. Am. Chem. Soc. 1995, 117, 5889.
17. (c) Quan, R. W.; Li, Z.; Jacobsen, E. N. J. Am. Chem. Soc. 1996, 118, 8156.
18. Meisenheimer, J.; Horing, M. Berichte 1927, 60, 1425.
19. 2 = 2.131. Data were collected on a Siemens SMART CCD. The structures were solved by direct methods with additional light atoms found by Fourier methods.
20. Nishio, M.; Umezawa, Y.; Hirota, M.; Takeuchi, Y. Tetrahedron 1995, 51, 8665.
21. Burley, S. K.; Petsko, G. A. Science 1985, 229, 23.
22. Jorgenson, W.; Severance, D. L. J. Am. Chem. Soc. 1990, 112, 4768.
23. 2 (0.025 mmol) were placed in a 25 mL round-bottom flask with proligand (0.055 mmol) and dichloromethane (10 mL) was added under an atmosphere of argon. The mixture was stirred for 10 min before chromene 5 (5.0 mmol) was added. The solution was stirred for a further 20 min before PhINTs (1.0 mmol) was added in one batch. After the specified interval the solution was filtered through a plug of silica gel, and the product was separated from excess chromene using flash chromatography on silica gel using hexane: ethyl acetate (6:1). Enantiomeric excess was readily determined using chiral HPLC (Chiralcel OD).
24. Södergren, M. J.; Alonso, D. A.; Bedekar, A. V.; Andersson, P. G. Tettrahedron Lett. 1997, 38, 6897.
25. 3/Cu(I) gave 40% ee and 45% yield overnight.
26. 2 (entry 7). See refs 5, 6. Lowering the temperature to -40 °C led to a further improvement in enantioselectivity (entries 8, 9).
27. Kitamura, M.; Suga, S.; Oka, H.; Noyori, R. J. Am. Chem. Soc. 1998, 120, 9800.
28. 6)], we would expect, on the basis of control experiments, the turnover rates to be very much lower. The recent synthesis of soluble PhINTs analogues will allow us to make direct kinetic investigations in this system: Macikenas, D.; Skrzypczak-Jankun, E.; Protasiewicz, J. D. J. Am. Chem. Soc. 1999, 121, 7164.