Olefin metathesis in the ionic liquid 1-butyl-3-methylimidazolium hexafiuorophosphate using a recyclable Ru catalyst: Remarkable effect of a designer ionic tag

Angewandte Chemie - International Edition

Volumn 42, Issue 29, 2003, Pages 3395-3398

  Yao, Qingwei ^a   Zhang, Yiliang ^a  

^a NORTHERN ILLINOIS UNIVERSITY   (United States)

Author keywords

Carbene complexes; Homogeneous catalysis; Ionic liquids; Metathesis; Ruthenium

Indexed keywords

CATALYSTS; ORGANIC SOLVENTS; RUTHENIUM;

IONIC LIQUIDS;

OLEFINS;

1 BUTYL 3 METHYLIMIDAZOLIUM HEXAFLUOROPHOSPHATE; ALKADIENE; ALKENE; CARBENE; IMIDAZOLE DERIVATIVE; ION; RUTHENIUM; SOLVENT; UNCLASSIFIED DRUG;

AQUEOUS SOLUTION; ARTICLE; CATALYSIS; CATALYST; CHEMICAL STRUCTURE; ENVIRONMENTAL PROTECTION; LIQUID; REACTION ANALYSIS; RECYCLING; RING CLOSING METATHESIS;

ALKENES; CATALYSIS; CYCLIZATION; IMIDAZOLES; IONS; MODELS, CHEMICAL; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; RUTHENIUM; SOLVENTS; STEREOISOMERISM;

EID: 0043031400     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200351222     Document Type: Article

References (64)

1. For selected recent reviews and monographs on green chemistry, see a) "Green Chemistry: Designing Chemistry for the Environment": ACS Symp. Ser. 1996, 626; b) Green Chemistry: Theory and Practice (Eds.: P. T. Anastas, J. Warner), Oxford University Press, New York, 1998; c) Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes (Eds.: P. T Anastas, T C. Williamson), Oxford University Press, New York, 1999.
2. For selected recent reviews and monographs on green chemistry, see a) "Green Chemistry: Designing Chemistry for the Environment": ACS Symp. Ser. 1996, 626; b) Green Chemistry: Theory and Practice (Eds.: P. T. Anastas, J. Warner), Oxford University Press, New York, 1998; c) Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes (Eds.: P. T Anastas, T C. Williamson), Oxford University Press, New York, 1999.
3. For selected recent reviews and monographs on green chemistry, see a) "Green Chemistry: Designing Chemistry for the Environment": ACS Symp. Ser. 1996, 626; b) Green Chemistry: Theory and Practice (Eds.: P. T. Anastas, J. Warner), Oxford University Press, New York, 1998; c) Green Chemistry: Frontiers in Benign Chemical Syntheses and Processes (Eds.: P. T Anastas, T C. Williamson), Oxford University Press, New York, 1999.
4. For general discussions on homogeneous catalysts and their heterogenization, see a) Applied Homogeneous Catalysis with Organometallic Compounds (Eds.: B. Cornil, W. A. Hermann) Wiley-VCH, Weiheim, 1996, chap. 3.1; b) Chiral Catalyst Immobilization and Recycling (Eds.: D. E. De Vos, I. F. J. Vankelecom, P. A. Jacobs), Wiley-VCH, Weiheim, 2000; c) N. E. Leadbeater, M. Marco, Chem. Rev. 2002, 102, 3217.
5. For general discussions on homogeneous catalysts and their heterogenization, see a) Applied Homogeneous Catalysis with Organometallic Compounds (Eds.: B. Cornil, W. A. Hermann) Wiley-VCH, Weiheim, 1996, chap. 3.1; b) Chiral Catalyst Immobilization and Recycling (Eds.: D. E. De Vos, I. F. J. Vankelecom, P. A. Jacobs), Wiley-VCH, Weiheim, 2000; c) N. E. Leadbeater, M. Marco, Chem. Rev. 2002, 102, 3217.
6. For general discussions on homogeneous catalysts and their heterogenization, see a) Applied Homogeneous Catalysis with Organometallic Compounds (Eds.: B. Cornil, W. A. Hermann) Wiley-VCH, Weiheim, 1996, chap. 3.1; b) Chiral Catalyst Immobilization and Recycling (Eds.: D. E. De Vos, I. F. J. Vankelecom, P. A. Jacobs), Wiley-VCH, Weiheim, 2000; c) N. E. Leadbeater, M. Marco, Chem. Rev. 2002, 102, 3217.
7. Selected recent reviews on ionic liquids and their application in transition-metal-catalyzed reactions: a) T. Welton, Chem. Rev. 1999, 99, 2071; b) P. Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; Angew. Chem. Int. Ed. 2000, 39, 3772; c) R. Sheldon, Chem. Commun. 2001, 2399; d) J. Dupont, R. F. de Souza, P. A. Suarez, Chem. Rev. 2002, 102, 3667.
8. Selected recent reviews on ionic liquids and their application in transition-metal-catalyzed reactions: a) T. Welton, Chem. Rev. 1999, 99, 2071; b) P. Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; Angew. Chem. Int. Ed. 2000, 39, 3772; c) R. Sheldon, Chem. Commun. 2001, 2399; d) J. Dupont, R. F. de Souza, P. A. Suarez, Chem. Rev. 2002, 102, 3667.
9. Selected recent reviews on ionic liquids and their application in transition-metal-catalyzed reactions: a) T. Welton, Chem. Rev. 1999, 99, 2071; b) P. Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; Angew. Chem. Int. Ed. 2000, 39, 3772; c) R. Sheldon, Chem. Commun. 2001, 2399; d) J. Dupont, R. F. de Souza, P. A. Suarez, Chem. Rev. 2002, 102, 3667.
10. Selected recent reviews on ionic liquids and their application in transition-metal-catalyzed reactions: a) T. Welton, Chem. Rev. 1999, 99, 2071; b) P. Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; Angew. Chem. Int. Ed. 2000, 39, 3772; c) R. Sheldon, Chem. Commun. 2001, 2399; d) J. Dupont, R. F. de Souza, P. A. Suarez, Chem. Rev. 2002, 102, 3667.
11. Selected recent reviews on ionic liquids and their application in transition-metal-catalyzed reactions: a) T. Welton, Chem. Rev. 1999, 99, 2071; b) P. Wasserscheid, W. Keim, Angew. Chem. 2000, 112, 3926; Angew. Chem. Int. Ed. 2000, 39, 3772; c) R. Sheldon, Chem. Commun. 2001, 2399; d) J. Dupont, R. F. de Souza, P. A. Suarez, Chem. Rev. 2002, 102, 3667.
12. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
13. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
14. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
15. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
16. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
17. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
18. Selected reviews on olefin metathesis: a) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124; Angew. Chem. Int. Ed. Engl. 1997, 36, 2036; b) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371; c) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413; d) A. Fürstner, Angew. Chem. 2000, 112, 3140; Angew. Chem. Int. Ed. 2000, 39, 3012; e) T. M. Trnka, R. H. Grubbs, Acc. Chem. Res. 2001, 34, 18.
19. P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1996, 118, 100.
20. a) M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953;
21. for related catalysts, b) see M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247;
22. c) J. Huang, E. D. Stevens, S. P. Nolan, J. F. Petersen, J. Am. Chem. Soc. 1999, 121, 2674.
23. a) J. S. Kingsbury, J. P. A. Harrity, P. J. Bonitatebus, A. H. Hoveyda, J. Am. Chem. Soc. 1999, 121, 791;
24. b) S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 8168;
25. for related catalysts, see c) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 832; Angew. Chem. Int. Ed. 2002, 41, 794;
26. for related catalysts, see c) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 832; Angew. Chem. Int. Ed. 2002, 41, 794;
27. d) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 2509; Angew. Chem. Int. Ed. 2002, 41, 2403;
28. d) H. Wakamatsu, S. Blechert, Angew. Chem. 2002, 114, 2509; Angew. Chem. Int. Ed. 2002, 41, 2403;
29. e) K. Crela, S. Harutyunyan, A. Michrowska, Angew. Chem. 2002, 114, 4210; Angew. Chem. Int Ed. 2002, 41, 4038.
30. e) K. Crela, S. Harutyunyan, A. Michrowska, Angew. Chem. 2002, 114, 4210; Angew. Chem. Int Ed. 2002, 41, 4038.
31. Q. Yao, Angew. Chem. 2000, 112, 4060; Angew. Chem. Int. Ed. 2000, 39, 3896.
32. Q. Yao, Angew. Chem. 2000, 112, 4060; Angew. Chem. Int. Ed. 2000, 39, 3896.
33. a) S. T. Nguyen, R. H. Grubbs, J. Organomet. Chem. 1995, 497, 195;
34. b) M. Ahmed, A. G. M. Barrett, D. C. Braddock, S. M. Cramp, P. A. Procopiou, Tetrahedron Lett. 1999, 40, 8657;
35. c) M. Ahmed, T. Arnauld, A. G. M. Barrett, D. C. Braddock, P. A. Procopiou, Synlett 2000, 1007;
36. d) S. C. Schürer, S. Gessler, N. Buschmann, S. Blechert, Angew. Chem. 2000, 112, 4062; Angew. Chem. Int. Ed. 2000, 39, 3898;
37. d) S. C. Schürer, S. Gessler, N. Buschmann, S. Blechert, Angew. Chem. 2000, 112, 4062; Angew. Chem. Int. Ed. 2000, 39, 3898;
38. e) L. Jafarpour, S. P. Nolan, Org. Lett. 2000, 2, 4075;
39. f) J. Dowden, J. Savovic, Chem. Commun. 2001, 37;
40. g) M. Mayr, B. Mayr, M. R. Buchmeiser, Angew. Chem. 2001, 113, 3957; Angew. Chem. Int. Ed. 2001, 40, 3839;
41. g) M. Mayr, B. Mayr, M. R. Buchmeiser, Angew. Chem. 2001, 113, 3957; Angew. Chem. Int. Ed. 2001, 40, 3839;
42. h) J. S. Kingsbury, S. B. Garber, J. M. Giftos, B. L. Gray, M. M. Okamoto, R. A. Farrer, J. T. Fourkas, A. H. Hoveyda, Angew. Chem. 2001, 113, 4381; Angew. Chem. Int. Ed. 2001, 40, 4251;
43. h) J. S. Kingsbury, S. B. Garber, J. M. Giftos, B. L. Gray, M. M. Okamoto, R. A. Farrer, J. T. Fourkas, A. H. Hoveyda, Angew. Chem. 2001, 113, 4381; Angew. Chem. Int. Ed. 2001, 40, 4251;
44. i) S. Randl, N. Buschmann, S. J. Connon, S. Blechert, Synlett 2001, 10, 1547;
45. j) L. Jafarpour, M. P. Heck, C. Baylon, H. L. Lee, C. Mioskowski, S. P. Nolan, Organometallics 2002, 21, 671;
46. k) S. J. Connon, A. M. Dunne, S. Blechert, Angew. Chem. 2002, 114, 3835; Angew. Chem. Int. Ed. 2002, 41, 3989;
47. k) S. J. Connon, A. M. Dunne, S. Blechert, Angew. Chem. 2002, 114, 3835; Angew. Chem. Int. Ed. 2002, 41, 3989;
48. l) K. Crela, M. Tryznowski, M. Bieniek, Tetrahedron Lett. 2002, 43, 9055;
49. m) S. Gibson, V. M. Swamy, Adv. Synth. Catal. 2002, 344, 619;
50. n) M. Mayr, M. R. Buchmeiser, K. Wurst, Adv. Synth. Catal. 2002, 344, 712.
51. 6 can either be purchased from Acros Organics at a relatively low cost or readily made in large quantities by simple procedures.
52. a) R. C. Buijsman, E. van Vuuren, J. G. Sterrenburg, Org. Lett. 2001, 3, 3785;
53. b) D. Semeril, H. Olivier-Bourbigou, C. Bruneau, P. H. Dixneuf, Chem. Commun. 2002, 146;
54. c) K. G. Mayo, E. H. Nearhoof, J. J. Kiddle, Org. Lett. 2002, 4, 1567;
55. d) S. Csihony, C. Fischmeister, C. Bruneau, I. T Horvath, P. H. Dixneuf, New J. Chem. 2002, 26, 1667.
56. 2 under vacuum first, followed by extraction of the product and any starting material with diethyl ether.
57. 1H NMR spectroscopy, which indicated a 98% conversion of the diene. A similar reaction was performed using the recovered ionic liquid. Only 22% of the added diene was found to be converted into the cyclized product.
58. 3): δ = 152.9, 149.6, 136.0, 131.6 129.2, 123.5, 122.0, 117.1, 114.8, 114.4, 111.9, 72.3, 67.4, 49.8, 36.2, 27.0, 25.8, 22.2 ppm.
59. The presence of free iodide in the reaction media may adversely effect the activity of Grubbs-type Ru catalysts as a result of potential ligand exchange, see a) E. L. Dias, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1997, 119, 3887; b) M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 6543.
60. The presence of free iodide in the reaction media may adversely effect the activity of Grubbs-type Ru catalysts as a result of potential ligand exchange, see a) E. L. Dias, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1997, 119, 3887; b) M. S. Sanford, J. A. Love, R. H. Grubbs, J. Am. Chem. Soc. 2001, 123, 6543.
61. 2Ru: C 48.11, H 6.50, N 3.12; found: C 48.09, H 6.45, N 3.05.
62. Q. Yao, Org. Lett. 2002, 4, 428.
63. Q. Yao, Org. Lett. 2001, 3, 2069.
64. M. Mori, N. Sakakibara, A. Kinoshita, J. Org. Chem. 1998, 63, 6082.