Palladium-catalyzed asymmetric allylic amination using ferrocenyl pyrazole ligands: Steric control of η3-allyl configuration and site-selective nucleophilic attack

Journal of the American Chemical Society

Volumn 118, Issue 5, 1996, Pages 1031-1037

  Togni, Antonio ^a   Burckhardt, Urs ^a   Gramlich, Volker ^a   Pregosin, Paul S ^a   Salzmann, Renzo ^a  

^a ETH ZURICH   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

METAL COMPLEX; PALLADIUM COMPLEX; PYRAZOLE DERIVATIVE;

ARTICLE; CATALYSIS; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS; X RAY DIFFRACTION;

EID: 0029928380     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja953031g     Document Type: Article

References (65)

1. For reviews, see: (a) Consiglio, G.; Waymouth, R. M. Chem. Rev. 1989, 89, 257-276. (b) Hayashi, T. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; pp 325-365. (c) Godleski, S. A. In Comprehensive Organic Synthesis: Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991: Vol. 4, Chapter 3.3, pp 585-661. (d) Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089-1122.
2. For reviews, see: (a) Consiglio, G.; Waymouth, R. M. Chem. Rev. 1989, 89, 257-276. (b) Hayashi, T. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; pp 325-365. (c) Godleski, S. A. In Comprehensive Organic Synthesis: Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991: Vol. 4, Chapter 3.3, pp 585-661. (d) Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089-1122.
3. For reviews, see: (a) Consiglio, G.; Waymouth, R. M. Chem. Rev. 1989, 89, 257-276. (b) Hayashi, T. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; pp 325-365. (c) Godleski, S. A. In Comprehensive Organic Synthesis: Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991: Vol. 4, Chapter 3.3, pp 585-661. (d) Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089-1122.
4. For reviews, see: (a) Consiglio, G.; Waymouth, R. M. Chem. Rev. 1989, 89, 257-276. (b) Hayashi, T. In Catalytic Asymmetric Synthesis; Ojima, I., Ed.; VCH: New York, 1993; pp 325-365. (c) Godleski, S. A. In Comprehensive Organic Synthesis: Trost, B. M., Fleming, I., Eds.; Pergamon: Oxford, 1991: Vol. 4, Chapter 3.3, pp 585-661. (d) Frost, C. G.; Howarth, J.; Williams, J. M. J. Tetrahedron: Asymmetry 1992, 3, 1089-1122.
5. For a recent review, see: Togni, A.; Venanzi, L. M. Angew. Chem., Int. Ed. Engl. 1994, 33, 497-526 (Angew. Chem. 1994, 106, 517-548).
6. For a recent review, see: Togni, A.; Venanzi, L. M. Angew. Chem., Int. Ed. Engl. 1994, 33, 497-526 (Angew. Chem. 1994, 106, 517-548).
7. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
8. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
9. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
10. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
11. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
12. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
13. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
14. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
15. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
16. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
17. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
18. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
19. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
20. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
21. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
22. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
23. For recent pertinent examples, see: (a) Leutenegger, U.; Umbricht, G.; Fahrni, C.; von Matt, P.; Pfaltz, A. Tetrahedron 1992, 48, 2143-2156. (b) von Man, P.; Pfaltz, A. Angew. Chem., Int. Ed. Engl. 1993, 32, 566 (Angew. Chem. 1993, 105, 614). (c) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573. (d) Sprinz, J.; Helmchen, G. Tetrahedron Lett. 1993, 34, 1769-1772. (e) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Tetrahedron Lett. 1994, 35, 1523-1526. (f) Frost, C. G.; Williams, J. M. J. Tetrahedron Lett. 1993, 34, 2015-2018. (g) Dawson, G. J.; Frost, C. G.; Williams, J. M. J.; Coote, S. J. Tetrahedron Lett. 1993, 34, 7793-7796. (h) Frost, C. G.; Williams, J. M. J. Tetrahedron: Asymmetry 1993, 4, 1785-1788. (i) Bovens, M.; Togni, A.; Venanzi, L. M. J. Organomet. Chem. 1993, 451, C28-C31. (j) Kubota, H.; Nakajima, M.; Koga, K. Tetrahedron Lett. 1993, 34, 8135-8138. (k) Brown, J. M.; Hulmes, D. I.; Guiry, P. J. Tetrahedron 1994, 50, 4493-4506. (l) Brenchley, G.; Merifield, E.; Wills, M.; Fedouloff, M. Tetrahedron Lett. 1994, 35, 2791-2794. (m) Tanner, D.; Andersson, P. G.; Harden, A.; Somfai, P. Tetrahedron Lett. 1994, 35, 4631-4634. (n) Gamez, P.; Dunjic, B.; Fache, M.; Lemaire, M. J. Chem. Soc. Chem. Commun. 1994, 1417-1418. (o) Kang, J.; Cho, W. O.; Cho, H. G. Tetrahedron: Asymmetry 1994, 5, 1347-1352. (p) von Matt, P.; Lloyd-Jones, G. C.; Minidis, A. B. E.; Pfaltz, A.; Macko, L.; Neuburger, M.; Zehnder, M.; Rüegger, H.; Pregosin, P. S. Helv. Chim. Acta 1995, 78, 265-284.
24. 3-allyl intermediate with the absolute configuration of the product. This is a typical ground-state argument, as it has been previously put forward by Bosnich; see: (a) Auburn, P. R.; Mackenzie, P. B.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2033-2046. (b) Mackenzie, P. B.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2046-2054. An alternative way of directing the incoming nucleophile by means of secondary interactions with a functional group contained in the ligands has been developed by Hayashi and Ito. For a review, see: Sawamura, M.; Ito, Y. Chem. Rev. 1992, 92, 857-871, and references cited therein.
25. 3-allyl intermediate with the absolute configuration of the product. This is a typical ground-state argument, as it has been previously put forward by Bosnich; see: (a) Auburn, P. R.; Mackenzie, P. B.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2033-2046. (b) Mackenzie, P. B.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2046-2054. An alternative way of directing the incoming nucleophile by means of secondary interactions with a functional group contained in the ligands has been developed by Hayashi and Ito. For a review, see: Sawamura, M.; Ito, Y. Chem. Rev. 1992, 92, 857-871, and references cited therein.
26. 3-allyl intermediate with the absolute configuration of the product. This is a typical ground-state argument, as it has been previously put forward by Bosnich; see: (a) Auburn, P. R.; Mackenzie, P. B.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2033-2046. (b) Mackenzie, P. B.; Whelan, J.; Bosnich, B. J. Am. Chem. Soc. 1985, 107, 2046-2054. An alternative way of directing the incoming nucleophile by means of secondary interactions with a functional group contained in the ligands has been developed by Hayashi and Ito. For a review, see: Sawamura, M.; Ito, Y. Chem. Rev. 1992, 92, 857-871, and references cited therein.
27. 3k indicated the significance of repulsive steric interactions in a late transition state.
28. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
29. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
30. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
31. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
32. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
33. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
34. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
35. For successful approaches utilizing 1,3-disubstituted acyclic allylic substrates, see: (a) Hayashi, T.; Yamamoto, A.; Ito, Y.; Nishioka, E.; Miura, H.; Yanagi, K. J. Am. Chem. Soc. 1989, 111, 6301-6311. (b) Hayashi, T.; Kishi, K.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1990, 31, 1743-1746. (c) Hayashi, T.; Yamamoto, A.; Ito, Y. Tetrahedron Lett. 1988, 29, 99-102. (d) von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Tetrahedron: Asymmetry 1994, 5, 573-584. Furthermore, Trost and co-workers developed the amination of cyclic allylic substrates, based on the enantiotopic group differentiation. See: (e) Trost, B. M.; Van Vranken, D. L.; Bingel, C. Angew. Chem.. Int. Ed. Engl. 1992, 31, 228-229 (Angew. Chem. 1992, 104, 194-196). (f) Trost, B. M.; Van Vranken, D. L.; Bingel, C. J. Am. Chem. Soc. 1992, 114, 9327-9343. (g) Trost, B. M.; Van Vranken, D. L. J. Am. Chem. Soc. 1993, 115, 444-458.
36. (a) Schnyder, A.; Hintermann, L.; Togni, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 931-933 (Angew. Chem. 1995, 107, 996-998).
37. (a) Schnyder, A.; Hintermann, L.; Togni, A. Angew. Chem., Int. Ed. Engl. 1995, 34, 931-933 (Angew. Chem. 1995, 107, 996-998).
38. (b) Burckhardt, U.; Hintermann, L.; Schnyder, A.; Togni, A. Organometallics 1995, 14, 5415-5425.
39. These reaction conditions correspond to those reported by Hayashi and co-workers, see ref 6a.
40. Assignment of the absolute configuration has been made by comparing the sign of the optical rotation with that reported in the literature (ref 6a).
41. For the observation of important electronic effects on stereoselectivity using this kind of ligands, see ref 7a.
42. A detailed account on the characterization and comparison of the structural features in solution, as obtained by 2D-NMR methods, is in preparation.
43. (a) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson, D. G.; Taylor, R. J. Chem. Soc., Dalton Trans. 1989, Supplement S1-S83.
44. (b) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen. A. G.; Taylor, R. J. Chem. Soc., Perkin Trans II 1987, Supplement S1-S19.
45. For a review see, e.g.; Appleton, T. G.; Clark, H. C.; Manzer, L. E. Coord. Chem. Rev. 1973, 10, 335-422.
46. For details concerning the application of NOESY spectroscopy to the structural characterization of Pd-allyl complexes in solution, see, e.g.: (a) Pregosin, P. S.; Salzmann, R.; Togni, A. Organometallics 1995, 14, 842-847. (b) Abbenhuis, H. C. L.; Burckhardt, U.; Gramlich, V.; Köllner, C.; Pregosin, P. S.; Salzmann, R.; Togni, A. Organometallics 1995, 14, 759-766, and pertinent references cited therein.
47. For details concerning the application of NOESY spectroscopy to the structural characterization of Pd-allyl complexes in solution, see, e.g.: (a) Pregosin, P. S.; Salzmann, R.; Togni, A. Organometallics 1995, 14, 842-847. (b) Abbenhuis, H. C. L.; Burckhardt, U.; Gramlich, V.; Köllner, C.; Pregosin, P. S.; Salzmann, R.; Togni, A. Organometallics 1995, 14, 759-766, and pertinent references cited therein.
48. A section of the phase-sensitive NOESY spectrum showing this particular selective exchange occuring on the NMR time scale is provided as supporting information. A simple π-σ-π equilibrium could account for this interconversion.
49. Such an interconversion ought to display a high activation barrier since, if operating, it could not take place via simple π-σ-π-equilibria only but probably would also require an apparent rotation of the allyl ligand. This could occur, e.g., via a dissociation of the pyrazole fragment leading to a T-shaped intermediate, followed by a rotation around the Pd-P bond and reformation of the chelate ring, as recently reported by Gogoll, Bäckvall, and co-workers for analogous systems. See: Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.-E. J. Am. Chem. Soc. 1994, 116, 3631-3632.
50. (a) Åkermark, B.; Hansson, S.; Vitagliano, A. J. Am. Chem. Soc. 1990, 112, 4587-4588.
51. (b) Sjögren, M. P. T.; Hansson, S.; Norrby, P.-O.; Akermark, B.; Cucciolito, M. E.; Vitagliano, A. Organometallics 1992, 11, 3954-3964. For related studies, see also: (c) Hansson, S.; Norrby, P.-O.; Sjögren, M. P. T.; Åkermark, B.; Cucciolito, M. E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940-4948. (d) Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B.; Vitagliano, A. J. Organomet. Chem. 1987, 335, 133-142. (e) Brown, J. M.; MacIntyre, J. E. J. Chem. Soc., Perkin Trans. II 1985, 961-970. (f) Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.-E. J. Am. Chem. Soc. 1994, 116, 3631-3632.
52. (b) Sjögren, M. P. T.; Hansson, S.; Norrby, P.-O.; Akermark, B.; Cucciolito, M. E.; Vitagliano, A. Organometallics 1992, 11, 3954-3964. For related studies, see also: (c) Hansson, S.; Norrby, P.-O.; Sjögren, M. P. T.; Åkermark, B.; Cucciolito, M. E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940-4948. (d) Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B.; Vitagliano, A. J. Organomet. Chem. 1987, 335, 133-142. (e) Brown, J. M.; MacIntyre, J. E. J. Chem. Soc., Perkin Trans. II 1985, 961-970. (f) Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.-E. J. Am. Chem. Soc. 1994, 116, 3631-3632.
53. (b) Sjögren, M. P. T.; Hansson, S.; Norrby, P.-O.; Akermark, B.; Cucciolito, M. E.; Vitagliano, A. Organometallics 1992, 11, 3954-3964. For related studies, see also: (c) Hansson, S.; Norrby, P.-O.; Sjögren, M. P. T.; Åkermark, B.; Cucciolito, M. E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940-4948. (d) Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B.; Vitagliano, A. J. Organomet. Chem. 1987, 335, 133-142. (e) Brown, J. M.; MacIntyre, J. E. J. Chem. Soc., Perkin Trans. II 1985, 961-970. (f) Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.-E. J. Am. Chem. Soc. 1994, 116, 3631-3632.
54. (b) Sjögren, M. P. T.; Hansson, S.; Norrby, P.-O.; Akermark, B.; Cucciolito, M. E.; Vitagliano, A. Organometallics 1992, 11, 3954-3964. For related studies, see also: (c) Hansson, S.; Norrby, P.-O.; Sjögren, M. P. T.; Åkermark, B.; Cucciolito, M. E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940-4948. (d) Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B.; Vitagliano, A. J. Organomet. Chem. 1987, 335, 133-142. (e) Brown, J. M.; MacIntyre, J. E. J. Chem. Soc., Perkin Trans. II 1985, 961-970. (f) Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.-E. J. Am. Chem. Soc. 1994, 116, 3631-3632.
55. (b) Sjögren, M. P. T.; Hansson, S.; Norrby, P.-O.; Akermark, B.; Cucciolito, M. E.; Vitagliano, A. Organometallics 1992, 11, 3954-3964. For related studies, see also: (c) Hansson, S.; Norrby, P.-O.; Sjögren, M. P. T.; Åkermark, B.; Cucciolito, M. E.; Giordano, F.; Vitagliano, A. Organometallics 1993, 12, 4940-4948. (d) Akermark, B.; Zetterberg, K.; Hansson, S.; Krakenberger, B.; Vitagliano, A. J. Organomet. Chem. 1987, 335, 133-142. (e) Brown, J. M.; MacIntyre, J. E. J. Chem. Soc., Perkin Trans. II 1985, 961-970. (f) Gogoll, A.; Örnebro, J.; Grennberg, H.; Bäckvall, J.-E. J. Am. Chem. Soc. 1994, 116, 3631-3632.
56. A bipyridine system containing a triptycyl substituent has recently been described as "molecular brake", by virtue of a conformational change induced by the complexation to a metal ion that blocks the free rotation of the triptycyl fragment. See: Ross Kelly, T.; Bowyer, M. C.; Vijaya Bhaskar, K.; Bebbington, D.; Garcia, A.; Lang, F.; Kim, M. H.; Jette, M. P. J. Am. Chem. Soc. 1994, 116, 3657-3658.
57. We presume that the minor isomer adopts a different conformation of the chelate ring, thus allowing for a slow rotation of the triptycyl moiety on the NMR time-scale.
58. 3], see: Togni, A.; Rihs, G.; Pregosin, P. S.; Ammann, C. Helv. Chim. Acta 1990, 73, 723-732.
59. 3], see: Togni, A.; Rihs, G.; Pregosin, P. S.; Ammann, C. Helv. Chim. Acta 1990, 73, 723-732.
60. This important aspect has been brought to our attention by Dr. J. M. Brown, Oxford University, who observed similar distorsions for the system reported in ref 3k.
61. For a review of this principle, see: Hine, J. Adv. Phys. Org. Chem. 1977, 15, 1-61.
62. Blöchl, P. E.; Togni, A., manuscript in preparation.
63. Jeener, J.; Meier, B. H.; Bachmann, P.; Ernst, R. R. J. Chem. Phys. 1979, 71, 4546-4553.
64. Summers, M. F.; Marzilli, L. G.; Bax, A. J. Am. Chem. Soc. 1986, 108, 4285-4294.
65. Sklenár, V.; Miyashiro, H.; Zon, G.; Miles, H. T.; Bax. A. FEBS Lett. 1986, 208, 94-98.