Synthesis, reaction, and recycle of light fluorous Grubbs-Hoveyda catalysts for alkene metathesis

Journal of Organic Chemistry

Volumn 70, Issue 5, 2005, Pages 1636-1642

  Matsugi, Masato ^a   Curran, Dennis P ^a  

^a UNIVERSITY OF PITTSBURGH   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

EXTRACTION; MIXTURES; OLEFINS; RECYCLING; SILICA GEL; SYNTHESIS (CHEMICAL);

FLUOROUS SILICA GEL; GRUBBS-HOVEYDA CATALYSTS; METATHESIS; SOLID-PHASE EXTRACTION;

CATALYSTS;

ALKENE; PERFLEXANE;

ARTICLE; CATALYSIS; CATALYST; CHEMICAL REACTION; CHEMICAL STRUCTURE; PHOTOREACTIVITY; REACTION ANALYSIS; SOLID PHASE EXTRACTION; SYNTHESIS;

ALKENES; CATALYSIS; FLUORIDES; MOLECULAR STRUCTURE; ORGANOMETALLIC COMPOUNDS; RUTHENIUM;

EID: 14544270505     PISSN: 00223263     EISSN: None     Source Type: Journal    
DOI: 10.1021/jo048001n     Document Type: Article

References (50)

1. Curran, D. P.; Luo, Z. J. Am. Chem. Soc. 1999, 121, 9069-9072.
2. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
3. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
4. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
5. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
6. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
7. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
8. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
9. Representative fluorous reagents and scavengers: (a) Dobbs, A. P.; McGregor-Johnson, C. Tetrahedron Lett. 2002, 43, 2807-2810. (b) Dandapani, S.; Curran, D. P. Tetrahedron 2002, 58, 3855-3864. (c) Zhang, W.; Chen, C. H.-T.; Lu, Y.; Nagashima, T. Org. Lett. 2004, 6, 1473-1476. (d) Lindsley, C. W.; Zhao, Z.; Leister, W. H. Tetrahedron Lett. 2002, 43, 4225-4228. (e) Lindsley, C. W.; Zhao, Z. J.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 6319-6323. (f) Lindsley, C. W.; Zhao, Z.; Newton, R. C.; Leister, W. H.; Strauss, K. A. Tetrahedron Lett. 2002, 43, 4467-4470. (g) Zhang, W.; Curran, D. P.; Chen, C. H.-T. Tetrahedron 2002, 58, 3871-3875. (h) Zhang, W.; Chen, C. H.-T.; Nagashima, T. Tetrahedron Lett. 2003, 44, 2065-2068.
10. Fluorous solid-phase extractions use silica gel with a fluorocarbon bonded phase: (a) Curran, D. P. Synlett 2001, 1488-1496. (b) Zhang, W. Tetrahedron 2003, 59, 4475-4489. (c) Curran, D. P. Separations with Fluorous Silica Gel and Related Materials. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 101-127. (d) Curran, D. P. A User's Guide to Light Fluorous Chemistry. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 128-155.
11. Fluorous solid-phase extractions use silica gel with a fluorocarbon bonded phase: (a) Curran, D. P. Synlett 2001, 1488-1496. (b) Zhang, W. Tetrahedron 2003, 59, 4475-4489. (c) Curran, D. P. Separations with Fluorous Silica Gel and Related Materials. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 101-127. (d) Curran, D. P. A User's Guide to Light Fluorous Chemistry. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 128-155.
12. Fluorous solid-phase extractions use silica gel with a fluorocarbon bonded phase: (a) Curran, D. P. Synlett 2001, 1488-1496. (b) Zhang, W. Tetrahedron 2003, 59, 4475-4489. (c) Curran, D. P. Separations with Fluorous Silica Gel and Related Materials. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 101-127. (d) Curran, D. P. A User's Guide to Light Fluorous Chemistry. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 128-155.
13. Fluorous solid-phase extractions use silica gel with a fluorocarbon bonded phase: (a) Curran, D. P. Synlett 2001, 1488-1496. (b) Zhang, W. Tetrahedron 2003, 59, 4475-4489. (c) Curran, D. P. Separations with Fluorous Silica Gel and Related Materials. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 101-127. (d) Curran, D. P. A User's Guide to Light Fluorous Chemistry. In Handbook of Fluorous Chemistry; Gladysz, J., Horváth, I., Curran, D. P., Eds.; Wiley-VCH: Weinheim, Germany, 2004; pp 128-155.
14. (a) Curran, D. P.; Fischer, K.; Moura-Letts, G. Synlett 2004, 1379-1382.
15. (b) Cavazzini, M.; Pozzi, G.; Quici, S.; Maillard, D.; Sinou, D. Chem. Commun. 2001, 1220-1221.
16. (c) Zhang, Q.; Luo, Z.; Curran, D. P. J. Org. Chem. 2000, 65, 8866-8873.
17. (d) Croxtall, B.; Hope, E. G.; Stuart, A. M. Chem. Commun. 2003, 2430-2431.
18. (a) Grubbs, R. H. Handbook of metathesis; WiLey-VCH: Weinheim, Germany, 2003.
19. (b) Furstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043.
20. (c) Furstner, A. Alkene metathesis in organic synthesis; Springer: New York, 1998.
21. Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus. P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
22. Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168-8179.
23. Leading reference: Zaja, M.; Connon, S. J.; Dunne, A. M.; Rivard, M.; Buschmann, N.; Jiricek, J.; Blechert, S. Tetrahedron 2003, 59, 6545-6558.
24. (a) Nguyen, S. T.; Johnson, L. K.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1992, 114, 3974-3975.
25. (b) Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1993, 115, 9858-9859.
26. (c) Wu, Z.; Nguyen, S. T.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1995, 117, 5503-5511.
27. (d) Schwab, P.; France, M. B.; Ziller, J. W.; Grubbs, R. H. Angew. Chem., Int. Ed. Engl. 1995, 34, 2039-2041.
28. (e) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
29. (a) Nguyen, S. T.; Trnka, T. M. In Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, Germany, 2003; Vol. 1, pp 61-94.
30. (b) Harned, A. M.; Probst, D. A.; Hanson, P. R. In Handbook of Metathesis; Grubbs, R. H., Ed.; Wiley-VCH: Weinheim, Germany, 2003; Vol. 2, pp 361-402.
31. Yao, Q.; Zhang, Y. J. Am. Chem. Soc. 2004, 126, 74-75.
32. Maruoka, K.; Sano, H.; Fukutani, Y.; Yamamoto, H. Chem. Lett. 1985, 1689-1692.
33. Aimetti, J. A.; Hamanaka, E. S.; Johnson, D. A.; Kellogg, M. S. Tetrahedron Lett. 1979, 20, 4631-4634.
34. Williard, P. G.; Fryhle, C. B. Tetrahedron Lett. 1980, 21, 3731-3734.
35. Audic, N.; Clavier, H.; Mauduit, M.; Guillemin, J.-C. J. Am. Chem. Soc. 2003, 125, 9248-9249.
36. Stille, J. K. Angew. Chem., Int. Ed. Engl. 1986, 25, 508-524.
37. Connon, S. J.; Blechert, S. Angew. Chem., Int. Ed. 2003, 42, 1900-1923.
38. 2Si) bonded phase. (b) DPC holds an equity interest in this company.
39. Tosyl amide 10 (1.00 g, 3.98 mmol) and 4a (211 mg, 0.199 mmol, 0.050 equiv) and dichloromethane (79.6 mL, 0.05 M) were placed in a flask under an argon atmosphere and the mixture was refluxed for 2 h at 55°C. After removal of the volatile components by evaporation, the brownish mixture was submitted to separation by fspe. A short column was packed with fluorous silica gel (6.3 g) using acetonitrile as the solvent. The crude reaction mixture was then loaded onto this column and eluted with 31.5 mL of acetonitrile to give RCM product 11 in 98% yield (865 mg). The next elution of diethyl ether (94.5 mL) afforded the catalyst 4a in 87% yield (184 mg).
40. Tosyl amide 10 (300 mg, 1.20 mmol) and 5 (64.2 mg, 0.060 mmol, 0.050 equiv) and dichloromethane (24 mL, 0.05 M) were placed in a flask under an argon atmosphere and the mixture was refluxed for 2 h at 55°C. After removal of the volatile components by evaporation, the brownish mixture was submitted to separation by fspe. A short column was packed with fluorous silica gel (3.2 g) using aq 80% MeOH as the solvent. The crude reaction mixture was then loaded onto this column and eluted with 16.1 mL of aq 80% MeOH and successively 9.7 mL of THF. The evaporation of the 80% MeOH fraction and the THF fraction by vacuum centrifuge gave RCM product 11 in 96% yield (256 mg) and catalyst 5 in 91% yield (58.3 mg), respectively.
41. A control experiment with standard catalyst 1 (14 mg) and 10 (119 mg) provided 109 mg of crude product 11 (>100%). This was a dark brown solid and was contaminated with 0.56% ruthenium, corresponding to 25% of the original amount of ruthenium added. Surprisingly, 10 mg (71%) of the original catalyst was recovered from the fluorous spe. The TLC results (Figure 2) suggest that the catalyst should not be retained, so this may be due to precipitation during spe loading or elution.
42. The crude product 11 was light tan and contained 0.46% Ru by elemental analysis (19% of original catalyst charge; however, there may be an error in this analysis since 91% of the original catalyst mass was recovered). The chromatographed product was a white powder containing <0.09% Ru while the crystallized product was a very pale tan powder containing <0.05% Ru.
43. (a) Chaterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11, 360-11, 370.
44. (b) Fürstner, A.; Ackermann L.; Gabor, B.; Goddard, R.; Lehmann, C. W.; Mynott, R.; Stelzer, F.; Thiel, O. R. Chem. Eur. J. 2001, 7, 3236-3253.
45. (a) Schwinn, D.; Glatz, H.; Bannwarth, W. Helv. Chim. Acta 2003, 86, 188-195.
46. (b) Tzschucke, C. C.; Markert, C.; Glatz, H.; Bannwarth, W. Angew. Chem., Int. Ed. 2002, 41, 4500-4503.
47. (c) Wende, M.; Meier, R.; Gladysz, J. A. J. Am. Chem. Soc. 2001, 123, 11490-11491.
48. (d) Wende, M.; Gladysz, J. A. J. Am. Chem. Soc. 2003, 125, 5861-5872.
49. (e) Jenkins, P. M.; Steele, A. M.; Tsang, S. C. Catal. Commun. 2003, 4, 45-50.
50. See Fluoruos Technolgies, Inc. Product Application Note "Fluorous Solid-Phase Extraction": http://fluorous.com/download.html.