Highly Active Trialkoxymolybdenum(VI) Alkylidyne Catalysts Synthesized by A Reductive Recycle Strategy

Journal of the American Chemical Society

Volumn 126, Issue 1, 2004, Pages 329-335

  Zhang, Wei ^a   Kraft, Stefan ^a,b   Moore, Jeffrey S ^a  

^a UNIVERSITY OF ILLINOIS AT URBANA CHAMPAIGN   (United States)

^b KANSAS STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

CATALYSIS; CATALYSTS; DIMERS; SOLVENTS; SYNTHESIS (CHEMICAL);

ALCOHOLYSIS;

MOLYBDENUM COMPOUNDS;

1,2,4 TRICHLOROBENZENE; 4 NITROPHENOL; ALCOHOL; ALKYNE; BUTANE; DIMER; LIGAND; MOLYBDENUM COMPLEX; PHENOL DERIVATIVE; PROPANE; SOLVENT; TRISAMIDOMOLYBDENUM PROPYLIDYNE COMPLEX; UNCLASSIFIED DRUG;

ALCOHOLYSIS; ARTICLE; CATALYSIS; PROTON NUCLEAR MAGNETIC RESONANCE; REDUCTION; RING CLOSING METATHESIS; ROOM TEMPERATURE; STEREOSPECIFICITY;

EID: 0347760004     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja0379868     Document Type: Article

References (80)

1. For reviews, see: (a) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18-29.
2. (b) Fürstner, A. Angew. Chem., Int. Ed. 2000, 39, 3012-3043.
3. (c) Grubbs, R. H.; Chang, S. Tetrahedron 1998, 54, 4413-4450.
4. (d) Schuster, M.; Blechert, S. Angew. Chem., Int. Ed. 1997, 36, 2037-2056.
5. (e) Fürstner, A. Top. Catal. 1997, 4, 285-299.
6. (f) Maier, M. E. Angew. Chem., Int. Ed. 2000, 39, 2073-2077.
7. (g) Schrock, R. R. Tetrahedron 1999, 55, 8141-8153.
8. (h) Schrock, R. R.; Hoveyda, A. H. Angew. Chem., Int. Ed. 2003, 42, 4592-4633.
9. For natural product synthesis, see: (a) Fürstner, A.; Guth, O.; Rumbo, A.; Seidel, G. J. Am. Chem. Soc. 1999, 121, 11108-11113.
10. (b) Fürstner, A.; Rumbo, A. J. Org. Chem. 2000, 65, 2608-2611.
11. (c) Fürstner, A.; Grela, K.; Mathes, C.; Lehmann, C. W. J. Am. Chem. Soc. 2000, 122, 11799-11805.
12. (d) Fürstner, A.; Radkowski, J.; Writz, C.; Mynott, R. J. Org. Chem. 2000, 65, 8758-8762.
13. (e) Fürstner, A.; Mathes, C.; Lehmann, C. W. Chem.-Eur. J. 2001, 7, 5299-5317.
14. (f) Fürstner, A.; Castanet, A.-S.; Radkowski, K.; Lehmann, C. W. J. Org. Chem. 2003, 68, 1521-1528.
15. (g) Fürstner, A.; Dierkes, T. Org. Lett. 2000, 2, 2463-2465.
16. (h) Fürstner, A.; Mathes, C.; Grela, K. Chem. Commun. 2001, 12, 1057-1059.
17. (i) Fürstner, A.; Stelzer, F.; Rumbo, A.; Krause, H. Chem.-Eur. J. 2002, 8, 1856-1871.
18. For polymer synthesis, see: (j) Weiss, K.; Michel, A.; Auth, E.-M.; Bunz, U. H. F.; Mangel, T.; Mullen, L. Angew. Chem., Int. Ed. Engl. 1997, 36, 506-509.
19. (k) Kloppenburg, L.; Song, D.; Bunz, U. H. F. J. Am. Chem. Soc. 1998, 120, 7973-7974.
20. (l) Bunz, U. H. F. Acc. Chem. Res. 2001, 34, 998-1010.
21. The alkylidyne mechanism was proposed by Katz and experimentally established by Schrock; see: (a) Katz, T. J.; McGinnis, J. J. Am. Chem. Soc. 1975, 97, 1592-1594.
22. (b) Wengrovius, J. H.; Sancho, J.; Schrock, R. R. J. Am. Chem. Soc. 1981, 103, 3932-3934.
23. (c) Bencheick, A.; Petit, M.; Mortreux, A.; Petit, F. J. Mol. Catal. 1982, 15, 93-101.
24. (a) Kerschner, J. L.; Fanwick, P. E.; Rothwell, I. P. J. Am. Chem. Soc. 1988, 110, 8235-8238.
25. (b) Kaneta, N.; Hirai, T.; Mori, M. Chem. Lett. 1995, 627-628.
26. (a) Mortreux, A.; Blanchard, M. J. Chem. Soc., Chem. Commun. 1974, 786-787.
27. (b) Kaneta, N.; Hirai, T.; Mori, M. Chem. Lett. 1995, 1055-1056.
28. (c) Vosloo, H. C. M.; du Plessis, J. A. K. J. Mol. Catal. A: Chem. 1998, 133, 205-211.
29. 6 that is simple and of wider applicability. See: Grela, K.; Ignatowska, J. Org. Lett, 2002, 4, 3747-3749.
30. Zhang, W.; Kraft, S.; Moore, J. S. Chem. Commun. 2003, 832-833.
31. 3; see: (a) Laplaza, C. E.; Odom, A. L.; Davis, W. M.; Cummins, C. C.; Protasiewicz, J. D. J. Am. Chem. Soc. 1995, 117, 4999-5000.
32. (b) Cummins, C. C. Chem. Commun. 1998, 1777-1786.
33. (c) Johnson, A. R.; Cummins, C. C.; Gambarotta, S. Inorg. Synth. 1998, 32, 123-132.
34. (d) Tsai, Y.-C.; Stephens, F. H.; Meyer, K.; Mendiratta, A.; Gheorghiu, M. D.; Cummins, C. C. Organometallics 2003, 22, 2902-2913.
35. 3; see: (e) Stoffelbach, F.; Saurenz, D.; Poli, R. Eur. J. Inorg. Chem. 2001, 2699-2703.
36. Fürstner, A.; Mathes, C.; Lehmann, C. W. J. Am. Chem. Soc. 1999, 121, 9453-9454.
37. Several combinations of reducing agents and solvent were examined, but magnesium in THF is the most effective. A zinc-copper couple, manganese, and samarium slowly produced 3 at 50 °C, but unknown side products also formed. At 70 °C, monochloride 2 decomposed quickly which makes the reductive recycle strategy not applicable at high temperature. Also see ref 6.
38. Triamide 1 was treated with 2 equiv of 1,1-dichloropropane instead of 15 equiv in order to minimize a side product which presumably arises from a Grignard reaction. Also see ref 6.
39. (a) McCullough, L. G.; Schrock, R. R. J. Am. Chem. Soc. 1984, 106, 4067-4068.
40. (b) McCullough, L. G.; Schrock, R. R.; Dewan, J. C.; Murdzek, J. C. J. Am. Chem. Soc. 1985, 107, 5987-5998.
41. (c) Murdzek, J. S.; Schrock, R. R. Carbyne Complexes; VCH: New York, 1988.
42. (d) Tsai, Y.-C.; Diaconescu, P. L.; Cummins, C. C. Organometallics 2000, 19, 5260-5262.
43. (e) Blackwell, J. M.; Figueroa, J. S.; Stephens, F. H.; Cummins, C. C. Organometallics 2003, 22, 3351-3353.
44. 19F NMR. See Supporting Information.
45. (a) King, A. O.; Okukado, N.; Negishi, E. J. Chem. Soc., Chem. Commun. 1977, 683-684.
46. (b) King, A. O.; Negishi, E.; Villani, F. J., Jr.; Silveira, A., Jr. J. Org. Chem. 1978, 43, 358-360.
47. (c) Negishi, E. Acc. Chem. Res. 1982, 15, 340-348.
48. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron Lett. 1975, 4467-4470.
49. (b) Sonogashira, K.; Yatake, T.; Tohda, Y.; Takahashi, S.; Hagihara, N. J. Chem. Soc., Chem. Commun. 1977, 291-292.
50. (c) Sonogashira, K. In Handbook of Organopalladium Chemistry for Organic Synthesis; Negishi, E., Ed.; Wiley-Interscience: New York, 2002; pp 493-529.
51. Vacuum conditions have been used for alkene/alkyne metathesis polymerization. See: Wagener, K. B.; Boncella, J. M.; Nell, J. G.; Duttweiler, R. P.; Hillmyer, M. A. Makromol. Chem. 1990, 191, 365-374 and ref 2j.
52. (a) Pschirer, N. G.; Bunz, U. H. F. Tetrahedron Lett. 1999, 40, 2481-2484.
53. (b) Fürstner, A.; Mathes, C. Org. Lett. 2001, 3, 221-223 and ref 2e.
54. 215MoO(OH) (2063.60): C, 83.23; H, 10.55. Found: C. 83.99; H, 10.66.
55. In closed systems, the ratio of product dimer-to-monomer reaching a constant value does not necessarily mean the reaction has reached equilibrium. We reasoned that metathesis of 9a-f and 11d did not reach the equilibrium due to catalyst poisoning by butyne polymerization and kinetically disfavored bulky intermediates. However, metathesis of butynyl substituted compounds 12a-f proceeded further, and no side reactions or intermediates were detected. In these examples, equilibrium is likely reached. This notion was further supported by the results of the forward and backward metathesis of 9f and 13. In both systems, a pathway-independent ratio of product dimer-to-monomer was observed, indicating that equilibrium had been attained. Variation in equilibrium constants may also explain the different product-to-starting material ratios in metathesis reactions of propynyl or butynyl substituted analogues.
56. Schrock, R. R. Polyhedron 1995, 14, 3177-3195.
57. The equilibrium position was determined by conducting the metathesis reaction in both forward (starting from 13) and backward (starting from 14 and 3-hexyne) directions. In both cases, the same ratio (2:3) of dimer to monomer was obtained.
58. 3 (15) providing trialkoxymolybdenum alkylidyne complexes 16 with free aniline; see ref 11d and e.
59. (a) Schrock, R. R.; Clark, D. N.; Sancho, J.; Wengrovius, J. H.; Rocklage, S. M.; Pedersen, S. F. Organometallics 1982, 1, 1645-1651.
60. (b) Listemann, M. L.; Schrock, R. R. Organometallics 1985, 4, 74-83.
61. (c) Schrock, R. R. Acc. Chem. Res. 1986, 19, 342-348.
62. (d) Freudenberger, J. H.; Schrock, R. R.; Churchill, M. R.; Rheingold, A. L.; Ziller, J. W. Organometallics 1984, 3, 1563-1573.
63. (a) Peters, J. C.; Odom, A. L.; Cummins, C. C. Chem. Commun. 1997, 1995-1996.
64. (b) Greco, J. B.; Peters, J. C.; Baker, T. A.; Davis, W. M.; Cummins, C. C.; Wu, G. J. Am. Chem. Soc. 2001, 123, 5003-5013.
65. (c) Agapie, T.; Diaconescu, P. L.; Cummins, C. C. J. Am. Chem. Soc. 2002, 124, 2412-2413.
66. Schrock reported that terminal alkynes are unsuitable in alkyne metathesis, which may be explained by the propensity of terminal alkylidynes to suffer ligand loss along the reaction pathway. See ref 19 and 22a-c. Recently it was reported by Fürstner that the terminal alkylidyne 3 exhibited poor metathesis activity. Using pure 3, we have followed up on this observation using 10 mol % 3 in the metathesis of 2-butynylbenzene with 11% conversion achieved, and we conclude that 3 is catalytically inactive.
67. Based on the same idea of a coordinating effect, 2-propynylthiophene substrate is problematic, which could partially be due to its high coordinative character. However, the fact that metathesis occurs in THF and MeCN and that 2-butynylthiophene undergoes metathesis indicates the coordination of these molecules is reversible and the affinity of the Mo center to alkynes is high.
68. (a) Bunz, U. H. F. Chem. Rev. 2000, 100, 1605-1644.
69. (b) Roncali, J. Acc. Chem. Res. 2000, 33, 147-156.
70. (c) Garnier, F. Acc. Chem. Res. 1999, 32, 209-215.
71. (d) Hayashi, H.; Yamamoto, T. Macromolecules 1997, 30, 330-332.
72. (e) Rutherford, D. R.; Stille, J. K.; Elliott, C. M. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 1990, 31, 643-644.
73. Polymerization of alkynes by a tungsten carbyne catalyst was reported before. See: (a) Weiss, K.; Goller, R.; Lössel, G. J. Mol. Catal. 1988, 46, 267-275.
74. (b) Bunz, U. H. F.; Kloppenburg, L. Angew. Chem., Int. Ed. 1999, 38, 478-481.
75. (c) Katz, T. J.; Ho, T. H.; Shih, N. Y.; Ying, Y. C.; Stuart, V. I. W. J. Am. Chem. Soc. 1984, 106, 2659-2668 and ref 3b.
76. Propynyl substituted compounds are the most commonly used substrates in alkyne metathesis in recent literature. See refs 2e,k, 4b, 8, 11d, and 16.
77. The same trend of reactivity was observed before by Schrock using W/Mo carbyne catalysts. See ref 11b.
78. For current synthesis and studies, see: (a) Nelson, J. C.; Saven, J. G.; Moore, J. S.; Wolynes, P. G. Science 1997, 277, 1793-1796.
79. (b) Brunsveld, L.; Meijer, E. W.; Prince, R. B.; Moore, J. S. J. Am. Chem. Soc. 2001, 123, 7978-7984.
80. (c) Prince, R. B.; Barnes, S. A.; Moore, J. S. J. Am. Chem. Soc. 2000, 122, 2758-2762.