Comparative investigation of ruthenium-based metathesis catalysts bearing N-heterocyclic carbene (NHC) ligands

Chemistry - A European Journal

Volumn 7, Issue 15, 2001, Pages 3236-3253

  Fürstner, Alois ^a   Ackermann, Lutz ^a   Gabor, Barbara ^a   Goddard, Richard ^a   Lehmann, Christian W ^a   Mynott, Richard ^a   Stelzer, Frank ^a   Thiel, Oliver R ^a  

^a MAX PLANCK INSTITUT FÜR KOHLENFORSCHUNG   (Germany)

Author keywords

Carbenes; Imidazol 2 ylidenes; IR thermography; Metathesis; Ruthenium

Indexed keywords

CATALYSTS; ISOMERIZATION; X RAY CRYSTALLOGRAPHY;

METATHESIS CATALYSTS;

RUTHENIUM;

CARBENOID; HETEROCYCLIC COMPOUND; IMIDAZOL 2 YLIDENE; IMIDAZOLE DERIVATIVE; LIGAND; RUTHENIUM DERIVATIVE; UNCLASSIFIED DRUG;

ARTICLE; CATALYST; COMPLEX FORMATION; CRYSTAL STRUCTURE; ELECTRONICS; INFRARED PHOTOGRAPHY; ISOMERISM; NUCLEAR MAGNETIC RESONANCE; STRUCTURE ACTIVITY RELATION; X RAY CRYSTALLOGRAPHY;

EID: 0035800494     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/1521-3765(20010803)7:15<3236::AID-CHEM3236>3.0.CO;2-S     Document Type: Article

References (132)

1. a) S. T. Nguyen, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1993, 115, 9858-9859;
2. b) S. T. Nguyen, L. K. Johnson, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1992, 114, 3974-3975;
3. c) P. Schwab, R. H. Grubbs, J. W. Ziller, J. Am. Chem. Soc. 1996, 118, 100-110.
4. Recent reviews: a) A. Fürstner, Angew. Chem. 2000, 112, 3140-3172;
5. Angew. Chem. Int. Ed. 2000, 39, 3012-3043;
6. b) R. H. Grubbs, S. Chang, Tetrahedron 1998, 54, 4413-4450;
7. c) A. Fürstner, Top. Organomet. Chem. 1998, 1, 37-72;
8. d) S. K. Armstrong, J. Chem. Soc. Perkin Trans. 1 1998, 371-388;
9. e) M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2124-2144;
10. Angew. Chem. Int. Ed. Engl. 1997, 36, 2037-2056;
11. f) A. Fürstner, Top. Catal. 1997, 4, 285-299;
12. g) K. J. Ivin, J. C. Mol, Olefin Metathesis and Metathesis Polymerization, Academic Press, San Diego, 1997.
13. a) J. Wolf, W. Stüer, C. Grünwald, H. Werner, P. Schwab, M. Schulz, Angew. Chem. 1998, 110, 1165-1167;
14. Angew. Chem. Int. Ed. 1998, 37, 1124-1126;
15. b) T. R. Belderrain, R. H. Grubbs, Organometallics 1997, 16, 4001-4003;
16. c) T. E. Wilhelm, T. R. Belderrain, S. N. Brown, R. H. Grubbs, Organometallics 1997, 16, 3867-3869.
17. a) E. L. Dias, S. T. Nguyen, R. H. Grubbs, J. Am. Chem. Soc. 1997, 119, 3887-3897;
18. b) O. M. Aagaard, R. J. Meier, F. Buda, J. Am. Chem. Soc. 1998, 120, 7174-7182;
19. c) C. Hinderling, C. Adlhart, P. Chen, Angew. Chem. 1998, 110, 2831-2835;
20. Angew. Chem. Int. Ed. 1998, 37, 2685-2689.
21. a) A. Fürstner, M. Picquet, C. Bruneau, P. H. Dixneuf, Chem. Commun. 1998, 1315-1316;
22. b) A. Fürstner, M. Liebl, C. W. Lehmann, M. Picquet, R. Kunz, C. Bruneau, D. Touchard, P. H. Dixneuf, Chem. Eur. J. 2000, 6, 1847-1857;
23. c) A. Demonceau, A. W. Stumpf, E. Saive, A. F. Noels, Macromolecules 1997, 30, 3127-3136;
24. d) A. Hafner, A. Mühlebach, P. A. van der Schaaf, Angew. Chem. 1997, 109, 2213-2216;
25. Angew. Chem. Int. Ed. Engl. 1997, 36, 2121-2124;
26. e) A. Fürstner, L. Ackermann, Chem. Commun. 1999, 95-96;
27. f) S. M. Hansen, M. A. O. Volland, F. Rominger, F. Eisenträger, P. Hofmann, Angew. Chem. 1999, 111, 1360-1364;
28. Angew. Chem. Int. Ed. 1999, 38, 1273-1276;
29. g) S. M. Hansen, F. Rominger, M. Metz, P. Hofmann, Chem. Eur. J. 1999, 5, 557-566;
30. h) H. Katayama, F. Ozawa, Organometallics 1998, 17, 5190-5196;
31. i) A. Fürstner, A. F. Hill, M. Liebl, J. D. E. T. Winton-Ely, Chem. Commun. 1999, 601-602;
32. j) M. Ahmed, A. G. M. Barrett, D. C. Braddock, S. M. Cramp, P. A. Procopiou, Tetrahedron Lett. 1999, 40, 8657-8662.
33. a) S. Chang, L. Jones, C. Wang, L. M. Henling, R. H. Grubbs, Organometallics 1998, 17, 3460-3465;
34. b) E. L. Dias, R. H. Grubbs, Organometallics 1998, 17, 2758-2767;
35. c) M. S. Sanford, L. M. Henling, R. H. Grubbs, Organometallics 1998, 17, 5384-5389;
36. d) J. S. Kingsbury, J. P. A. Harrity, P. J. Bonitatebus, A. H. Hoveyda, J. Am. Chem. Soc. 1999, 121, 791-799.
37. a) J. Huang, E. D. Stevens, S. P. Nolan, J. L. Pedersen, J. Am. Chem. Soc. 1999, 121, 2674-2678;
38. b) J. Huang, H.-J. Schanz, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 5375-5380.
39. a) M. Scholl, T. M. Trnka, J. P. Morgan, R. H. Grubbs, Tetrahedron Lett. 1999, 40, 2247-2250;
40. b) M. Scholl, S. Ding, C. W. Lee, R. H. Grubbs, Org. Lett. 1999, 1, 953-956.
41. a) L. Ackermann, A. Fürstner, T. Weskamp, F. J. Kohl, W. A. Herrmann, Tetrahedron Lett. 1999, 40, 4787-4790;
42. b) T. Weskamp, F. J. Kohl, W. Hieringer, D. Gleich, W. A. Herrmann, Angew. Chem. 1999, 111, 2573-2576;
43. Angew. Chem. Int. Ed. 1999, 38, 2416-2419;
44. c) U. Frenzel, T. Weskamp, F. J. Kohl, W. C. Schattenmann, O. Nuyken, W. A. Herrmann, J. Organomet. Chem. 1999, 586, 263-265.
45. For reviews see: a) W. A. Hermann, C. Köcher, Angew. Chem. 1997, 109, 2256-2282;
46. Angew. Chem. Int. Ed. Engl. 1997, 36, 2162-2187;
47. b) D. Bourissou, O. Guerret, F. P. Gabbai, G. Bertrand, Chem. Rev. 2000, 100, 39-91;
48. c) A. J. Arduengo, Acc. Chem. Res. 1999, 32, 913-921;
49. 3 bonds see: J. Huang, H.-J. Schanz, E. D. Stevens, S. P. Nolan, Organometallics 1999, 18, 2370-2375.
50. A. Fürstner, O. R. Thiel, L. Ackermann, H.-J. Schanz, S. P. Nolan, J. Org. Chem. 2000, 65, 2204-2207.
51. A. K. Chatterjee, J. P. Morgan, M. Scholl, R. H. Grubbs, J. Am. Chem. Soc. 2000, 122, 3783-3784.
52. a) L. Ackermann, D. El Tom, A. Fürstner, Tetrahedron 2000, 56, 2195-2202;
53. b) A. Fürstner, O. R. Thiel, N. Kindler, B. Bartkowska, J. Org. Chem. 2000, 65, 7990-7995;
54. c) A. Fürstner, O. R. Thiel, G. Blanda, Org. Lett. 2000, 2, 3731-3734;
55. d) A. Fürstner, O. R. Thiel, L. Ackermann, Org. Lett. 2001, 3, 449-451.
56. a) J. Limanto, M. L. Snapper, J. Am. Chem. Soc. 2000, 122, 8071-8072;
57. b) I. Efremov, L. A. Paquette, J. Am. Chem. Soc. 2000, 122, 9324-9325;
58. c) R. M. Garbaccio, S. J. Danishefsky, Org. Lett. 2000, 2, 3127-3129;
59. d) L. Hyldtoft, R. Madsen, J. Am. Chem. Soc. 2000, 122, 8444-8452;
60. e) J. C. J. Benningshof, R. H. Blaauw, A. E. van Ginkel, F. P. J. T. Rutjes, J. Fraanje, K. Goubitz, H. Schenk, H. Hiemstra, Chem. Commun. 2000, 1465-1466;
61. f) J. A. Smulik, S. T. Diver, Org. Lett. 2000, 2, 2271-2274;
62. g) D. L. Wright, J. P. Schulte, M. A. Page, Org. Lett. 2000, 2, 1847-1850;
63. h) C. W. Lee, R. H. Grubbs, Org. Lett. 2000, 2, 2145-2147;
64. i) R. Stragies, U. Voigtmann, S. Blechert, Tetrahedron Lett. 2000, 41, 5465-5468;
65. j) M. Ahmed, T. Arnauld, A. G. M. Barrett, D. C. Braddock, P. A. Procopiou, Synlett 2000, 1007-1009;
66. k) D. Bourgeois, J. Mahuteau, A. Pancrazi, S. P. Nolan, J. Prunet, Synthesis 2000, 869-882;
67. l) T. Itoh, K. Mitsukura, N. Ishida, K. Uneyama, Org. Lett. 2000, 2, 1431-1434;
68. m) A. Briot, M. Bujard, V. Gouverneur, S. P. Nolan, C. Mioskowski, Org. Lett. 2000, 2, 1517-1519.
69. A few structural variants of 2 and 3 have been reported, although all of them contain identical substituents on both N-atoms of the NHC ligand, cf. ref. [9] and the following: a) S. C. Schürer, S. Gessler, N. Buschmann, S. Blechert, Angew. Chem. 2000, 112, 4062-4065;
70. Angew. Chem. Int. Ed. 2000, 39, 3898-3901;
71. b) S. B. Garber, J. S. Kingsbury, B. L. Gray, A. H. Hoveyda, J. Am. Chem. Soc. 2000, 122, 8168-8179;
72. c) L. Jafarpour, E. D. Stevens, S. P. Nolan, J. Organomet. Chem. 2000, 606, 49-54.
73. A. J. Arduengo, R. Krafczyk, R. Schmutzler, H. A. Craig, J. R. Goerlich, W. J. Marshall, M. Unverzagt, Tetrahedron 1999, 55, 14523-14534.
74. a) A. J. Arduengo, F. Davidson, H. V. R. Dias, J. R. Goerlich, D. Khasnis, W. J. Marshall, T. K. Prakasha, J. Am. Chem. Soc. 1997, 119, 12742-12749;
75. b) A. J. Arduengo, H. V. R. Dias, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1992, 114, 5530-5534;
76. c) A. J. Arduengo, R. L. Harlow, M. Kline, J. Am. Chem. Soc. 1991, 113, 361-363.
77. W. A. Herrmann, C. Köcher, L. J. Gooßen, G. R. J. Artus, Chem. Eur. J. 1996, 2, 1627-1636.
78. M. G. Gardiner, W. A. Herrmann, C. P. Reisinger, J. Schwarz, M. Spiegler J. Organomet. Chem. 1999, 572, 239-247.
79. 2 formed, cf. ref. [17b]. If applicable, we prefer this method for its preparative convenience over an alternative procedure using NaH in liquid ammonia as the reaction medium, cf. ref. [18].
80. a) D. Enders, K. Breuer, G. Raabe, J. Runsink, J. H. Teles, J.-P. Melder, K. Ebel, S. Brode, Angew. Chem. 1995, 107, 1119-1122;
81. Angew. Chem. Int. Ed. Engl. 1995, 34, 1021-1023;
82. b) for a detailed description of the reactivity of this carbene, including its reactions with olefins see: D. Enders, K. Breuer, J. Runsink, J. H. Teles, Liebigs Ann. 1996, 2019-2028.
83. L. Jafarpour, S. P. Nolan, Organometallics 2000, 19, 2055-2057.
84. 2 using the parent-complex 1 see: A. Fürstner, D. Koch, K. Langemann, W. Leitner, C. Six, Angew. Chem. 1997, 109, 2562-2565;
85. Angew. Chem. Int. Ed. Engl. 1997, 36, 2466-2469.
86. 31P NMR spectra; 2D EXSY confirm that this effect is due to rotamers around the Ru-NHC bond.
87. R. O. Gould, A. M. Gray, P. Taylor, M. D. Walkinshaw, J. Am. Chem. Soc. 1985, 107, 5921-5927.
88. T. Weskamp, W. C. Schattenmann, M. Spiegler, W. A. Hermann, Angew. Chem. 1998, 110, 2631-2633;
89. Angew. Chem. Int. Ed. 1998, 37, 2490-2493.
90. C. W. Bielawski, R. H. Grubbs, Angew. Chem. 2000, 112, 3025-3028;
91. Angew. Chem. Int. Ed. 2000, 39, 2903-2906.
92. a) For a detailed discussion see ref.[11].
93. b) Note, that the decomposition of the catalyst also constitutes a potential source of ruthenium hydride species; although the decomposition pathways of the Grubbs catalyst 1 have been studied in some detail, the ruthenium species formed are not yet clear, cf.: M. Ulman, R. H. Grubbs, J. Org. Chem. 1999, 64, 7202-7207.
94. C. Grünwald, O. Gevert, J. Wolf, P. Gonzalez-Herrero, H. Werner, Organometallics 1996, 15, 1960-1962.
95. V. Rodriguez, S. Sabo-Etienne, B. Chaudret, J. Thoburn, S. Ulrich, H.-H. Limbach, J. Eckert, J.-C. Barthelat, K. Hussein, C. J. Marsden, Inorg. Chem. 1998, 37, 3475-3485.
96. 2, cf. S. D. Drouin, G. P. A. Yap, D. E. Fogg, Inorg. Chem. 2000, 39, 5412-5414.
97. According to our opinion some data reported in the literature are inadequate for an assessment of the reactivity of NHC containing catalysts. Complexes of this type were repeatedly applied to a single substrate such as diethyl diallylmalonate which reacts very smoothly even with the parent Grubbs carbene 1 and is therefore of limited value for probing the reactivity of more powerful catalysts.
98. a) A. Fürstner, K. Langemann, J. Org. Chem. 1996, 61, 3942-3943;
99. b) A. Fürstner, K. Langemann, Synthesis 1997, 792-803.
100. Monitoring of this transformation by GC and TLC shows that the formation of the cyclic monomer proceeds via an initial dimerization of substrate 25 at the monosubstituted alkene; the resulting dimer 26 is then converted into the cyclic monomer 27. For a more detailed report on this observation see ref. [13d].
101. Review: M. Mori, Top. Organomet. Chem. 1998, 1, 133-154.
102. See ref. [14f, i] and the following for leading references: a) A. Kinoshita, N. Sakakibara, M. Mori, J. Am. Chem. Soc. 1997, 119, 12388-12389;
103. b) R. Stragies, M. Schuster, S. Blechert, Angew. Chem. 1997, 109, 2628-2630;
104. Angew Chem. Int. Ed. Engl. 1997, 36, 2518-2520;
105. c) A. G. M. Barrett, S. P. D. Baugh, D. C. Braddock, K. Flack, V. C. Gibson, P. A. Procopiou, Chem. Commun. 1997, 1375-1376;
106. d) K. Hammer, K. Undheim, Tetrahedron 1997, 53, 10603-10614;
107. e) A. Kinoshita, M. Mori, Synlett 1994, 1020-1022;
108. f) M. Mori, T. Kitamura, N. Sakakibara, Y. Sato, Org. Lett. 2000, 2, 543-545;
109. g) M. Mori, N. Sakakibara, A. Kinoshita, J. Org. Chem. 1998, 63, 6082-6083;
110. h) J. A. Smulik, S. T. Diver, J. Org. Chem. 2000, 65, 1788-1792 and references therein.
111. While RCM is driven by the gain in entropy caused by the (gaseous) by-product (e.g. ethene) released during the course of the reaction, enyne metathesis is devoid of such an inherent driving force. Therefore most examples reported so far deal with the formation of five-membered rings which have the highest intrinsic bias for cyclization. For some successful applications to larger rings see ref. [36g].
112. 2 or electron deficient palladacycles as catalysts; for leading references see: a) N. Chatani, N. Furukawa, H. Sakurai, S. Murai, Organometallics 1996, 15, 901-903;
113. b) B. M. Trost, M. K. Trost, J. Am. Chem. Soc. 1991, 113, 1850-1852;
114. c) A. Fürstner, H. Szillat, B. Gabor, R. Mynott, J. Am. Chem. Soc. 1998, 120, 8305-8314;
115. d) A. Fürstner, H. Szillat, F. Stelzer, J. Am. Chem. Soc. 2000, 122, 6785-6786.
116. Leading references: a) M. T. Reetz, M. H. Becker, K. M. Kühling, A. Holzwarth, Angew. Chem. 1998, 110, 2792-2795;
117. Angew. Chem. Int. Ed. 1998, 37, 2647-2650;
118. b) A. Holzwarth, H.-W. Schmidt, W. F. Maier, Angew. Chem. 1998, 110, 2788-2792;
119. Angew. Chem. Int. Ed. 1998, 37, 2644-2647;
120. c) S. J. Taylor, J. P. Morken, Science 1998, 280, 267-270.
121. Reviews on combinatorial methods in catalysis: a) B. Jandeleit, D. J. Schaefer, T. S. Powers, H. W. Turner, W. H. Weinberg, Angew. Chem. 1999, 111, 2648-2689;
122. Angew. Chem. Int. Ed. 1999, 38, 2494-2532;
123. b) M. T. Reetz, Angew. Chem. 2001, 113, 292-320;
124. Angew. Chem. Int. Ed. 2001, 40, 284-310.
125. M. T. Reetz, M. H. Becker, M. Liebl, A. Fürstner, Angew. Chem. 2000, 112, 1294-1298;
126. Angew. Chem. Int. Ed. 2000, 39, 1236-1239.
127. For preparative applications of this complex see: a) A. Fürstner, O. R. Thiel, J. Org. Chem. 2000, 65, 1738-1742;
128. b) A. Fürstner, J. Grabowski, C. W. Lehmann, T. Kataoka, K. Nagai, ChemBioChem 2001, 2, 60-68;
129. c) A. Fürstner, J. Grabowski, C. W. Lehmann, J. Org. Chem. 1999, 64, 8275-8280;
130. d) A. Fürstner, K. Radkowski, Chem. Commun. 2001, 671-672.
131. -1 more stable than enyne 29. This explains the exothermicity observed by the thermocamera. It is believed, however, that the much more dramatic evolution of heat in case of complexes 3 and 10 as compared to the other catalysts screened is partly due to the fact that the heating of the reaction mixture caused by the incipient reaction increases the reaction rate, thereby producing even more heat and a yet faster conversion. Such an "autocatalytic" effect is absent whenever the reaction rate is such that heat transfer to the surroundings occurs at similar rates as the progress of the reaction.
132. Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307-326.