Nitro-substituted Hoveyda-Grubbs ruthenium carbenes: Enhancement of catalyst activity through electronic activation

Journal of the American Chemical Society

Volumn 126, Issue 30, 2004, Pages 9318-9325

  Michrowska, Anna ^a   Bujok, Robert ^a   Harutyunyan, Syuzanna ^a   Sashuk, Volodymyr ^a   Dolgonos, Grigory ^b   Grela, Karol ^a  

^a INSTITUTE OF ORGANIC CHEMISTRY   (Poland)

^b INSTITUTE OF PHYSICAL CHEMISTRY   (Poland)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; CHEMICAL ACTIVATION; CHEMICAL BONDS; ENZYMES; SUBSTITUTION REACTIONS; SYNTHESIS (CHEMICAL);

ELECTRON-DEFICIENT SUBSTRATES; METATHESIS;

RUTHENIUM COMPOUNDS;

CARBENE; RUTHENIUM DERIVATIVE;

ARTICLE; CATALYST; CHEMICAL ANALYSIS; CHEMICAL BOND; COMPLEX FORMATION; MOLECULAR STABILITY; RING CLOSING METATHESIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 3342982883     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja048794v     Document Type: Article

References (73)

1. Pertinent reviews: (a) Schrock, R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592-4633.
2. (b) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29.
3. (c) Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043.
4. (d) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
5. (e) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. Engl. 1997, 36, 2037-2056.
6. (f) Dragutan, V.; Dragutan, I.; Balaban, A. T. Platinum Metals Rev. 2001, 45, 155-163.
7. (a) Kingsbury, J. S.; Harrity, J. P. A.; Bonitatebus, P. J.; Hoveyda, A. H. J. Am. Chem. Soc. 1999, 121, 791-799.
8. (b) Garber, S. B.; Kingsbury, J. S.; Gray, B. L.; Hoveyda, A. H. J. Am. Chem. Soc. 2000, 122, 8168-8179.
9. For a short review on these catalysts, see: Hoveyda, A. H.; Gillingham, D. G.; Van Veldhuizen, J. J.; Kataoka, O.; Garber, S. B.; Kingsbury, J. S.; Harrity, J. P. A. Org. Biomol. Chem. 2004, 2, 1-16.
10. (a) Randl, S.; Gessler, S.; Wakamatsu, H.; Blechert, S. Synlett 2001, 430-432.
11. For activation of Grubbs's carbene 2b toward acrylonitrile, via either structural modifications or addition of CuCl, see: (b) Love, J. A.; Morgan, J. P.; Trnka, T. M.; Grubbs, R. H. Angew. Chem., Int. Ed. 2002, 41, 4035-4037.
12. (c) Rivard, M.; Blechert, S. Eur. J. Org. Chem. 2003, 2225-2228.
13. Imhof, S.; Randl, S.; Blechert, S. Chem. Commun. 2001, 1692-1693.
14. For syntheses of supported variants of 2, see inter alia ref 2b and (a) Kingsbury, J. S.; Garber, S. B.; Giftos, J. M.; Gray, B. L.; Okamoto, M. M.; Farrer, R. A.; Fourkas, J. T.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2001, 40, 4251-4255.
15. (b) Grela, K.; Tryznowski, M.; Bieniek, M. Tetrahedron Lett. 2002, 43, 9055-9059.
16. (c) Connon, S. J.; Dunne, A. M.; Blechert, S. Angew. Chem., Int. Ed. 2002, 41, 3835-3838.
17. (d) Dowden, J.; Savovic, J. Chem. Commun. 2001, 37-38.
18. (e) Yao, Q. Angew. Chem., Int. Ed. 2000, 39, 3896-3898.
19. (f) Yao Q.; Zhang, Y. Angew. Chem., Int. Ed. 2003, 42, 3395-3398.
20. (g) Connon, S. J.; Blechert, S. Bioorg. Med. Chem. Lett. 2002, 12, 1873-1876.
21. (h) Yao, Q.; Zhang, Y. J. Am. Chem. Soc. 2004, 12, 74-75.
22. (i) Yao, Q.; Motta, A. R. Tetrahedron Lett. 2004, 45, 2447-2451.
23. Catalysts 2 are commercially available from Aldrich Chemical Co.
24. For a comparison of relative initiation rates of lb and 2b, see refs 9a,b, 11, and 12.
25. (a) Wakamatsu, H.; Blechert, S. Angew. Chem., Int. Ed. 2002, 41, 794-796.
26. (b) Wakamatsu, H.; Blechert, S. Angew. Chem., Int. Ed. 2002, 41, 2403-2405.
27. (c) For an improved synthesis of 4b and reactivity studies, see: Dunne, A. M.; Mix, S.; Blechert, S. Tetrahedron Lett. 2003, 44, 2733-2736.
28. Extensive studies described in ref 9b,c suggest that a steric bulk adjacent to the chelating isopropoxy moiety of 3b and 4b is the crucial factor securing the unusually high activity of these complexes.
29. (a) Grela, K.; Kim, M. Eur. J. Org. Chem. 2003, 963-966.
30. (b) For a unique activity of a catalyst derived from 5 in living polymerization of diynes, see: Krause, J. O.; Zarka, M. T.; Anders, U.; Weberskirch, R.; Nuyken, O.; Buchmeiser, M. R. Angew. Chem., Int. Ed. 2003, 42, 5965-5969.
31. (a) Grela, K.; Harutyunyan, S.; Michrowska, A. Angew. Chem., Int. Ed. 2002, 41, 4038-4040.
32. For applications of 6b in target-oriented synthesis, see the following. (b) (-)-Securinine: Honda, T.; Namiki, H.; Kaneda, K.; Mizutani, H. Org. Lett. 2004, 6, 87-89.
33. (c) An artificial photosynthesis model: Ostrowski, S.; Mikus, A. Mol. Divers. 2003, 6, 315-321.
34. (d) Harutyunyan, S.; Michrowska, A.; Grela, K. In Catalysts for Fine Chemical Synthesis; Roberts, S., Ed; Wiley-Interscience: New York, 2004; Vol. 3, in press.
35. (a) After our report on 6b, another study on the effects of EWG and EDG substituents in the benzylidene part of 2 on the rate of metathesis was published: Zaja, M.; Connon, S. J.; Dunne, A. M.; Rivard, M.; Buschrnann, N.; Jiricek, J.; Blechert, S.Tetrahedron 2003, 59, 6545-6558.
36. (b) For an application of a CN-substituted Hoveyda-Grubbs catalyst, see: Connon, S. J.; Rivard, M.; Zaja, M.; Blechert, S. Adv. Synth. Catal. 2003, 345, 572-575.
37. 2 group and the increased electron deficiency at the initiating carbene species should make 6b more active in olefin metathesis.
38. 2 group, see: De Clercq, B.; Verpoort, F. Adv. Synth. Catal. 2002, 344, 639-648.
39. (c) Schwab, P.; Grubbs, R. H.; Ziller, J. W. J. Am. Chem. Soc. 1996, 118, 100-110.
40. See the Supporting Information for experimental details.
41. 2 group is twisted 22.1° off-plane. See the Supporting Information and ref 33 for computational details.
42. 2 group led to a complex that is 3 times more potent than an unmodified catalyst, a sterically hindered one acts more than 100 times faster in the same model reaction. However, both modes of activation can be successfully combined in this case, as the doubly (sterically and electronically) modified chiral complex possessed the highest level of potency among those studied. Van Veldhuizen, J. J.; Gillingham, D. G.; Garber, S. B.; Kataoka, O.; Hoveyda, A. H. J. Am. Chem. Soc. 2003, 125, 12502-12508.
43. For reviews on catalytic cross-metathesis, see: (a) Vemall, A. J.; Abell, A. D. Aldrichimica Acta 2003, 36, 93-105.
44. (b) Blechert, S.; Connon, S. J. Angew. Chem., Int. Ed. 2003, 42, 1900-1923.
45. (c) Blackwell, H. E.; O'Leary, D. J.; Chatterjee, A. K.; Washenfelder, R. A.; Bussmann, D. A.; Grubbs, R. H. J. Am. Chem. Soc. 2000, 122, 58-71.
46. (d) For a short review on applications to commercial products, see: Pederson, R. L.; Fellows, I. M.; Ung, T. A.; Ishihara, H.; Hajela, S. P. Adv. Synth. Catal. 2002, 344, 728-735.
47. (e) For a general model for selectivity in olefin CM, see: Chatterjee, A. K.; Choi, T.-L.; Sanders, D. P.; Grubbs, R. H. J. Am. Chem. Soc. 2003, 125, 11360-11370.
48. (a) Grela, K.; Bieniek, M. Tetrahedron Lett. 2001, 42, 6425-6428.
49. (b) Grela, K.; Michrowska, A.; Bieniek, M.; Kim, M.; Klajn, R. Tetrahedron 2003, 59, 4525-4531.
50. (c) For an application of this transformation in the enantioselective synthesis of furanone natural products, see: Evans, P.; Leffray, M. Tetrahedron 2003, 59, 7973-7981.
51. Sierra, M. A.; de la Torre, M. C. Angew. Chem., Int. Ed. 2000, 39, 1538-1559.
52. Ma̧kosza, M.; Stalewski, J.; Wojciechowski, K.; Danikiewicz, W. Tetrahedron 1997, 53, 193-214.
53. Demchuk, O. M.; Pietrusiewicz, K. M.; Michrowska, A.; Grela, K. Org. Lett. 2003, 5, 3217-3220.
54. 1H NMR spectra registered in the presence of (S)-N-[1-(1-naphthyl)ethyl]-3,5- dinitrobenzamide (Kagan shift reagent). Cf. ref. 22 and (a) Pakulski, Z.; Demchuk, O. M.; Kwiatosz, R.; Osiñski, P. W.; Wierczyñska, W.; Pietrusiewicz, K. M. Tetrahedron: Asymmetry 2003, 14, 1459-1462.
55. (b) Deshmukh, M.; Dunach, E.; Juge, S.; Kagan, H. B. Tetrahedron Lett. 1984, 25, 3467-3470.
56. The examples of metathesis between two electron-deficient olefins are rare, and good yields have been reported only for homodimerization of acrylates and for cross-metathesis of α,β-unsaturated substrates with styrenes. See: (a) Choi, T.-L.; Lee, C. W.; Chatterjee, A. K.; Grubbs, R. H. J. Am. Chem. Soc. 2001, 123, 10417-10418.
57. (b) Chatterjee, A. K.; Toste, F. D.; Choi, T.-L.; Grubbs, R. H. Adv. Synth. Catal. 2002, 344, 634-637.
58. Michrowska, A.; Szmigietska, A.; Demchuk, O. M.; Butenschön, H.; Pietrusiewicz, K. M.; Grela, K. Unpublished.
59. The similar lack of activity of 1b in homocoupling of vinylphosphine oxides has been reported independently: Bisaro, F.; Gouverneur, V. Tetrahedron Lett. 2003, 44, 7133-7135.
60. CM of terminal olefins and 2-methyl-2-butene, reported by Grubbs et al., constitutes a very elegant method of an allyl-to-prenyl conversion: Chatterjee, A. K.; Sanders, D. P.; Grubbs, R. H. Org. Lett. 2002, 4, 1939-1942.
61. Significantly higher yields in the cyclisation of dienes shown in Table 3 have been reported in the literature. (a) 61, 31% (5 mol % of 1b; 24 h in refluxing DCM; NMR yield): Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999, 1, 953-956.
62. (b) 59, 95% (5 mol % of 1c; toluene, 80 °C, 24 h; isolated yield); 61, 47% (5 mol % of 1c; toluene, 80 °C, 24 h; GC yield); 62, 75% (5 mol % of 1c; toluene, 80 °C, 18 h; isolated yield); cf.: 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.
63. (a) There are no separate reports devoted to applications of the Hoveyda-Grubbs catalysts for the preparation of tetrasubstituted C-C double bonds. However, Hoveyda et al. have noted that tetrasubstituted olefins were obtained less efficiently through catalytic RCM promoted by 2b (ref 2). For a possible explanation of the lower level of efficiency observed with 2b, see ref 3.
64. (b) For some examples of the formation of tetrasubstituted olefins with Hoveyda-type catalysts, see also ref 6b,h,i.
65. The complex 6b is stable up to 110 °C and efficiently promotes metathesis at 80 °C in toluene. Grela, K.; Bieniek, M. Unpublished. For the stability of 2b and 4b, see refs 2 and 9, respectively.
66. In general, the recyclability of 6b is handicapped as compared with that of 2b, and typically 6b can be recovered after metathesis reaction only with moderate efficiency. See the Supporting Information for the recovery experiments.
67. (a) Kitamura, T.; Sato, Y.; Mori, M. Adv. Synth. Catal. 2002, 344, 678-693.
68. (b) Kitamura, T.; Sato, Y.; Mori, M. Chem. Commun. 2001, 1258-1259.
69. All the calculations were performed using Gaussian 98 (Gaussian 98, Revision A.11.4; Gaussian, Inc.: Pittsburgh, PA, 2002) on an IRIX64/Linux workstation. The structures of 2-isopropoxystyrenes were optimized using B3LYP with the 6-31G** basis set. Only real values of the analytical harmonic vibrational frequencies confirmed that the geometries under study correspond to the minimum-energy structures.
70. Mulliken, R. S. J. Chem. Phys. 1955, 23, 1833.
71. For a full set of ESP/Mulliken charges, see the Supporting Information.
72. Similar changes in chemical shifts have been observed for another member of this series, compound 73: Ru=CH, 16.34 and 289.8; iPrO methine proton, 5.01 ppm, and carbon, 78.9 ppm. Arlt, D.; Bieniek, M.; Michrowska, A.; Bujok, R.; Grela K. Unpublished results.
73. For screening of the catalytic performance of catalysts lb, 2b, 4b, and 6b in the synthesis of cyclooctenes, see: Sibi, M. P.; Aasmul, M.; Hasegawa, H.; Subramanian, T. Org. Lett. 2003, 5, 2883-2886.