Phosphinooxazolines - A new class of versatile, modular P,N-ligands for asymmetric catalysis

Accounts of Chemical Research

Volumn 33, Issue 6, 2000, Pages 336-345

  Helmchen, Günter ^a   Pfaltz, Andreas ^b  

^a UNIVERSITY OF HEIDELBERG   (Germany)

^b UNIVERSITY OF BASEL   (Switzerland)

Author keywords

[No Author keywords available]

Indexed keywords

ALLYL COMPOUND; IMINE; KETONE DERIVATIVE; LIGAND; NITROGEN; ORGANOMETALLIC COMPOUND; ORGANOPHOSPHORUS COMPOUND; OXAZOLE DERIVATIVE; OXAZOLINE DERIVATIVE; PALLADIUM; PHOSPHINE; PHOSPHINE DERIVATIVE; PHOSPHINOOXAZOLINE DERIVATIVE; PHOSPHORUS; RUBIDIUM; UNCLASSIFIED DRUG;

ARTICLE; CATALYSIS; CHEMICAL REACTION; CHEMICAL STRUCTURE; CHEMISTRY; CONFORMATION; HYDROGENATION; LIGAND BINDING; REACTION ANALYSIS; STEREOCHEMISTRY; STEREOISOMERISM; STRUCTURE ACTIVITY RELATION; STRUCTURE ANALYSIS; SYNTHESIS;

CATALYSIS; LIGANDS; MOLECULAR CONFORMATION; ORGANOMETALLIC COMPOUNDS; ORGANOPHOSPHORUS COMPOUNDS; OXAZOLES; PALLADIUM; PHOSPHINES; RUBIDIUM; STEREOISOMERISM;

EID: 0033949478     PISSN: 00014842     EISSN: None     Source Type: Journal    
DOI: 10.1021/ar9900865     Document Type: Article

References (64)

1. 2 Symmetry and Asymmetric Induction. Chem. Rev. 1989, 89, 1581-1590.
2. 2-Symmetric Chiral Bis(oxazoline)-metal Complexes in Catalytic Asymmetric Synthesis. Tetrahedron: Asymmetry 1998, 9, 1-45.
3. 2-Symmetric Chiral Bis(oxazoline)-metal Complexes in Catalytic Asymmetric Synthesis. Tetrahedron: Asymmetry 1998, 9, 1-45.
4. + System. Organometallics 1984, 3, 1231-1240.
5. Review: Helmchen, G.; Kudis, S.; Sennhenn, P.; Steinhagen, H. Enantioselective Catalysis with Complexes of Asymmetric P,N-Chelate Ligands. Pure Appl. Chem. 1997, 69, 513-518.
6. 2-Symmetric Semicorrins and Bisoxazolines to Non-symmetric Phosphinooxazolines. Acta Chem. Scand. B 1996, 50, 189-194.
7. Review: Williams, J. M. J. The Ups and Downs of Allylpalladium Complexes in Catalysis. Synlett 1996, 705-710.
8. For other types of chiral P,N-ligands see ref 16b.
9. Gant, T. G.; Meyers, A. I. The Chemistry of 2-Oxazolines (1985-Present). Tetrahedron 1994, 50, 2297-2360.
10. Koch, G.; Lloyd-Jones, G. C.; Loiseleur, O.; Prétôt, R.; Pfaltz, A.; Schaffner, S.; Schnider, P.; von Matt, P. Synthesis of Chiral (Phosphinoaryl)oxazolines, a Versatile Class of Ligands for Asymmetric Catalysis. Recl. Trav. Chim. Pays-Bas 1995, 114, 206-210.
11. Originally, n-BuLi or s-BuLi in THF was used (ref 9). Subsequently we found that in n-hexane the yields are usually better (Schnider, P., Pfaltz, A., unpublished results).
12. (a) Peer, M.; de Jong, J. C.; Kiefer, M.; Langer, T.; Rieck, H.; Schell, H.; Sennhenn, P.; Sprinz, J.; Steinhagen, H.; Wiese, B.; Helmchen, G. Enantioselective Catalysis of Allylic Substitutions with Pd Complexes of Phosphinooxazolines. Tetrahedron 1996, 52, 7547-7583. See also ref 6.
13. (a) Sammakia, T.; Latham, H. A.; Schaad, D. R. Highly Diastereoselective Ortho Lithiations of Chiral Oxazoline-Substituted Ferrocenes. J. Org. Chem. 1995, 60, 10-11.
14. (b) Richards, C.; Damaldis, T.; Hibbs, D. E.; Hursthouse, M. B. Synthesis of 2-[2-(Diphenylphosphino)ferrocenyl]oxazoline Ligands. Synlett 1995, 74-76.
15. (c) Nishibayashi, Y.; Uemura, S. Synlett 1995, 79.
16. (d) Park, J.; Lee, S.; Ahn, K. H.; Cho, C.-W. Lithiation and Phosphorylation of Chiral 1,1′-Bis(oxazolinyl)ferrocenes. Tetrahedron Lett. 1995, 36, 7263-7266.
17. Kudis, S.; Helmchen, G. Enantioselective Allylic Substitution of Cyclic Substrates by Catalysis with Palladium Complexes of P,N-Chelate Ligands with a Cymantrene Unit. Angew. Chem., Int. Ed. 1998, 37, 3047-3050.
18. Imai, Y.; Zhang, W.; Kida, T.; Nakatsuji, Y.; Ikeda, I. Diphenylphosphinooxazoline Ligands with a Chiral Binaphthyl Backbone for Pd-Catalyzed Allylic Alkylation. Tetrahedron Lett. 1998, 39, 4343-4346.
19. (a) Evans, P. A.; Brandt, T. A. Enantioselective Allylic Substitution Using a Novel (Phosphino-1,3-oxazine)palladium Catalyst. Tetrahedron Lett. 1996, 37, 9143-9146.
20. (b) Kündig, E. P.; Meier, P. Synthesis of New Chiral Bidentate (Phosphinophenyl)benzoxazine P,N-Ligands. Helv. Chim. Acta 1999, 82, 1360-1370.
21. (a) Trost, B. M.; Van Vranken, D. L. Asymmetric Transition Metal-Catalyzed Allylic Alkylations. Chem. Rev. 1996, 96, 395-422.
22. (b) Lautens, M. A.; Pfaltz, A. Allylic Substitution Reactions. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, 1999; Vol. 2, Chapter 24.
23. Von Matt, P.; Loiseleur, O.; Koch, G.; Pfaltz, A.; Lefeber, C.; Feucht, T.; Helmchen, G. Enantioselective Allylic Amination with Chiral (phosphino-oxazoline)palladium Catalysts. Tetrahedron: Asymmetry 1994, 5, 573-584.
24. Blacker, A. J.; Clark, M. L.; Loft, M. S.; Williams, J. M. J. First Highly Enantioselective Allylic Alkylations Catalyzed by Platinum Complexes. Chem. Commun. 1999, 913-914.
25. For a detailed survey, see: Helmchen, G. Enantioselective Palladium-Catalyzed Allylic Substitutions with Asymmetric Chiral Ligands. J. Organomet. Chem. 1999, 576, 203-214.
26. (a) Sprinz, J.; Kiefer, M.; Helmchen, G.; Reggelin, M.; Huttner, G.; Walter, O.; Zsolnai, L. Catalysis of Allylic Substitutions by Pd Complexes of Oxazolines Containing an Additional P, S, or Se Center. X-ray Crystal Structures and Solution Structures of Chiral π-Allyl Palladium Complexes of Phosphinoaryloxazolines. Tetrahedron Lett. 1994, 35, 1523-1526.
27. 1 Allyl Isomerization in a Chiral Allylic Alkylation Catalyst. J. Am. Chem. Soc. 1994, 116, 4067-4068.
28. 0 Complex. Angew. Chem., Int. Ed. Engl. 1997, 36, 2108-2110.
29. Schaffner, S.; Müller, J. F. K.; Neuburger, M.; Zehnder, M. On the Origin of Asymmetric Induction of the Palladium-Catalyzed Allylic Substitution Reaction with Chiral 4,4-Disubstituted 4,5-Dihydro-2-(phosphinoaryl)oxazole Ligands. Helv. Chim. Acta 1998, 81, 1223-1232 and earlier work cited.
30. Wiese, B.; Helmchen, G. Chiral Phosphinooxazolines with a Bi-or Tricyclic Oxazoline Moiety - Applications in Pd-Catalyzed Allylic Alkylations. Tetrahedron Lett. 1998, 39, 5727-5730.
31. (a) Prétôt, R.; Lloyd-Jones, G. C.; Pfaltz, A. Enantio- and Regio-control in Palladium- and Tungsten-Catalyzed Allylic Substitutions. Pure Appl. Chem. 1998, 70, 1035-1040 and literature cited.
32. (b) Hilgraf, R.; Pfaltz, A. Chiral Bis(N-tosylamino)phosphine- and TADDOL-Phosphite-Oxazolines as Ligands in Asymmetric Catalysis. Synlett 1999, 1814-1816.
33. (c) See also: Hayashi, T.; Kawatsura, M.; Uozumi, Y. Regioselective and Enantioselective Allylic Alkylation Catalyzed by a Chiral Monophosphine-palladium Complex. Chem. Commun. 1997, 561-562.
34. Takeuchi, R.; Kashio, M. Highly Selective Allylic Alkylation with a Carbon Nucleophile at the More Substituted Allylic Terminus Catalyzed by an Iridium Complex: an Efficient Method for Constructing Quaternary Carbon Centers. Angew. Chem., Int. Ed. Engl. 1997, 36, 263-265.
35. Bartels, B.; Helmchen, G. Ir-Catalyzed Allylic Substitution: Mechanistic Aspects and Asymmetric Synthesis with Phosphorus Amidites as Ligands. Chem. Commun. 1999, 741-742 and literature cited.
36. (a) Trost, B. M.; Hachiya, I. Asymmetric Molybdenum-Catalyzed Alkylations. J. Am. Chem. Soc. 1998, 120, 1104-1105.
37. (b) Glorius, F.; Pfaltz, A. Enantioselective Molybdenum-Catalyzed Allylic Alkylation Using Chiral Bisoxazoline Ligands. Org. Lett. 1999, 1, 141-144.
38. (a) Koch, G.; Pfaltz, A. Chiral Phosphinooxazolines as Ligands in Asymmetric Catalysis: Intramolecular Pd-Catalyzed Allylic Alkylation. Tetrahedron: Asymmetry 1996, 7, 2213-2216. An incorrect absolute configuration is assigned to the product in this report.
39. (b) Helmchen, G.; Peer, M., unpublished.
40. Sudo, A.; Saigo, K. A Widely Applicable Chiral Auxiliary, cis-2-Amino-3,3-dimethyl-1-indanol: Conversion to a Novel Phosphorus-Containing Oxazoline and its Application as a Highly Efficient Ligand for the Palladium-Catalyzed Enantioselective Allylic Amination Reaction. J. Org. Chem. 1997, 62, 5508-5513.
41. Review: Loiseleur, O.; Hayashi, M.; Keenan, M.; Schmees, N.; Pfaltz, A. Enantioselective Heck Reactions Using Chiral P,N-Ligands. J. Organomet. Chem. 1999, 576, 16-22.
42. (a) Hayashi, T.; Kubo, A.; Ozawa, F. Catalytic asymmetric arylation of olefins. Pure Appl. Chem. 1992, 64, 421-427.
43. (b) Shibasaki, M.; Vogl, E. M. Heck Reaction. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, 1999; Chapter 14.
44. Ripa, L.; Hallberg, A. Intramolecular Enantioselective Palladium-Catalyzed Heck Arylation of Cyclic Enamides. J. Org. Chem. 1997, 62, 595-602.
45. (a) Knöbel, A. K. H.; Escher, I. H.; Pfaltz, A. Enantioselective Copper-Catalyzed 1,4-Addition of Organozinc Reagents to Enones Using Chiral Oxazoline-Phosphite Ligands. Synlett 1997, 1429-1431.
46. (b) Escher, I. H.; Pfaltz, A. Tetrahedron 2000, in press.
47. For other recent results in this area, see: Tomioka, K.; Nagaoka, Y. Conjugate Addition of Organometallic Reagents. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, 1999; Vol. 3, Chapter 31.1.
48. (a) Kainz, S.; Brinkmann, A.; Leitner, W.; Pfaltz, A. Iridium-Catalyzed Enantioselective Hydrogenation of Imines in Supercritical Carbon Dioxide. J. Am. Chem. Soc. 1999, 121, 6421-6429 and earlier work of the Pfaltz group cited.
49. (b) Lightfoot, A.; Schnider, P.; Pfaltz, A. Enantioselective Hydrogenation of Olefins with Iridium-phosphanodihydrooxazole Catalysts. Angew. Chem., Int. Ed. 1998, 37, 2897-2899.
50. Although excellent enantioselectivities could be achieved with titanocene and zirconocene catalysts, the turnover numbers and frequencies were low. Troutman, M. V.; Appella, D. H.; Buchwald, S. L. Asymmetric Hydrogenation of Unfunctionalized Tetrasubstituted Olefins with a Cationic Zirconocene Catalyst. J. Am. Chem. Soc. 1999, 121, 4916-4917 and literature cited.
51. Review: Palmer, M. J.; Wills, M. Asymmetric Transfer Hydrogenation of C:O and C:N Bonds. Tetrahedron: Asymmetry 1999, 10, 2045-2061.
52. 2-Symmetric Bioxazolines and Bithiazolines as New Chiral Ligands for Metal Ion Catalyzed Asymmetric Syntheses: Asymmetric Hydrosilylation. Synlett 1991, 257-259.
53. Langer, Th.; Helmchen, G. Highly Efficient New Catalysts for Enantioselective Transfer Hydrogenation of Ketones. Tetrahedron Lett. 1996, 37, 1381-1384.
54. Diploma theses at Universität Heidelberg by Reinhard, F., 1996; Nell, P., 1996; and Pähler, S., 1996.
55. Diploma theses at Universität Heidelberg by Reinhard, F., 1996; Nell, P., 1996; and Pähler, S., 1996.
56. Diploma theses at Universität Heidelberg by Reinhard, F., 1996; Nell, P., 1996; and Pähler, S., 1996.
57. (a) Sammakia, T.; Stangeland, E. L. Transfer Hydrogenation with Ruthenium Complexes of Chiral (Phosphinoferrocenyl)oxazolines. J. Org. Chem. 1997, 62, 6104-6105.
58. (b) Arikawa, Y.; Ueoka, M.; Matoba, K.; Nishibayashi, Y., Uemura, S. Ruthenium(II)-Catalyzed Asymmetric Transfer Hydrogenation of Ketones Using Chiral Oxazolinylferrocenylphosphines and one of their Ru(II) Complex. J. Organomet. Chem. 1999, 572, 163-168.
59. 3)(oxazolinylferrocenylphosphine). Organometallics 1999, 18, 2291-2293.
60. Jiang, Y.; Jiang, Q.; Zhu, G.; Zhang, X. Highly Effective NPN-Type Tridentate Ligands for Asymmetric Transfer Hydrogenation of Ketones. Tetrahedron Lett. 1997, 38, 215-218.
61. Review: Nishiyama, H. Hydrosilylation of Carbonyl and Imino Groups. In Comprehensive Asymmetric Catalysis; Jacobsen, E. N., Pfaltz, A., Yamamoto, H., Eds.; Springer: Heidelberg, 1999; Vol. 1, Chapter 6.3.
62. Aeby, A.; Bangerter F.; Consiglio, G. Enantioselective Dicarbonylation of Styrene to Isotactic Poly[1-oxo-2-phenylpropane-1,3-diyl] with Phosphinodihydrooxazole-palladium(II) Complexes. Model Studies for Enantioface Selection. Helv. Chim. Acta 1998, 81, 764-769 and literature cited.
63. Uozumi, Y.; Kato, K.; Hayashi, T. Asymmetric Aza-Claisen Rearrangement of Allyl Imidates Catalyzed by Homochiral Cationic Palladium(II) Complexes. Tetrahedron: Asymmetry 1998, 9, 1065-1072.
64. Sagasser, I.; Helmchen, G. (Phosphino-oxazoline)copper(II) Complexes as Chiral Catalysts for Enantioselective Diels-Alder Reactions. Tetrahedron Lett. 1998, 39, 261-264.