Mechanistic Studies of the Zirconium-Triisopropanolamine-Catalyzed Enantioselective Addition of Azide to Cyclohexene Oxide

Journal of Organic Chemistry

Volumn 63, Issue 19, 1998, Pages 6656-6666

  McCleland, Brent W ^a   Nugent, William A ^b   Finn, M G ^a  

^a UNIVERSITY OF VIRGINIA   (United States)

^b DUPONT COMPANY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EID: 0000931779     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo9809377     Document Type: Article

References (79)

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25. (b) A dimeric form of a related titanium alkyl hydroperoxide triethanolamine complex incorporating bridging alkoxide bonds has been crystallographically characterized: Boche, G.; Köbus, K.; Harms, K.; Marsch, M. J. Am. Chem. Soc. 1996, 118, 2770-2771.
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30. (d) For crystallographic characterizations of terminal metal azide complexes, see: Proulx, G.; Bergman, R. G. J. Am. Chem. Soc. 1995, 117, 6382-6383; Fickes, M. G.; Davis, W. M.; Cummins, C. C. J. Am. Chem. Soc. 1995, 117, 6384-6385.
31. Burger, B. J.; Bercaw, J. E. In Experimental Organometallic Chemistry: A Practicum in Synthesis and Characterization; Wayda, A. L.; Darensbourg, M. Y., Eds.; ACS Symposium Series 357; American Chemical Society: Washington, DC, 1987; Chapter 4, pp 94-95. We employ a slightly simpler one-piece glass apparatus that avoids the use of O-ring joints.
32. Finn, M. G.; Sharpless, K. B. J. Am. Chem. Soc. 1991, 113, 113-126.
33. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
34. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
35. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
36. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
37. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
38. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
39. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
40. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
41. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
42. These observations closely resemble the phenomenon of "non- linear" relationships between the enantiomeric composition of a chiral catalyst and the enantiomeric excess of its catalyzed process, first identified by Kagan and co-workers. For examples, see the following references, (a) Puchot, C.; Samuel, O.; Duñach, E.; Zhao, S.; Agami, C.; Kagan, H. B. J. Am. Chem. Soc. 1986, 108, 2353-2357. (b) Guillaneux, D.; Zhao, S.-H.; Samuel, O.; Rainford, D.; Kagan, H. B. J. Am. Chem. Soc. 1994, 116, 9430-9439. (c) Zhang, S. Y.; Girard, C.; Kagan, H. B. Tetrahedron: Asymmetry 1995, 6, 2637-2640, and references therein, (d) Kitamura, M.; Suga, S.; Niwa, M.; Noyori, R. J. Am. Chem. Soc. 1995, 117, 4832-4842; see also ref 30b. (e) Keck, G. E.; Krishnamurthy, D. J. Am. Chem. Soc. 1995, 117, 2363-2364. (f) Kitamoto, D.; Imma, H.; Nakai, T. Tetrahedron Lett. 1995, 36, 1861-1864. (g) Boyle, T. J.; Eilerts, N. W.; Heppert, J. A.; Takusagawa, F. Organometallics 1994, 13, 2218-2229. (h) Terada, M.; Mikami, T.; Nakai, T. J. Chem. Soc., Chem. Commun. 1990, 1623-1624. (i) Rossiter, B. R.; Eguchi, M.; Miao, G.; Swingle, N. M.; Hernandez, A. E.; Vickers, D.; Fluckiger, E.; Patterson, G.; Reddy, K. V. Tetrahedron 1993, 49, 965-986. (j) Komatsu, N.; Hashizume, M.; Sugita, T.; Uemura, S. J. Org. Chem. 1993, 58, 7624-7626. See also ref 28c.
43. A typical reaction resulting in a final ee of 82% starts out at approximately 60-65% ee over the first 1-2% of the reaction (corresponding approximately to one-half the amount of total zirconium) and then rises quickly to the steady-state value. The reaction rate varies similarly.
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47. 3- Si-containing product is 89%. In all cases involving sequential addition of silyl azides, enantiomeric excess for the first azide produced is 50-70%.
48. Assuming that no exchange of propanolamine ligands occurs, let x and y represent the rates of reaction catalyzed by the (S,S,S)- and (R,S,S)-complexes, respectively. Noting that the pure (S,S,S)- catalyst gives approximately 84% ee (92: 8 mixture of enantiomers), and the (R,S,S)-catalyst gives nearly racemic product, 70% ee = 85/15 = 1x.92 + 4y.50/1x.8 + 4y.50, which gives x/y = 20.
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