Dehydrogenation of n-alkanes catalyzed by iridium 'pincer' complexes: Regioselective formation of α-olefins

Journal of the American Chemical Society

Volumn 121, Issue 16, 1999, Pages 4086-4087

  Liu, Fuchen ^a   Pak, Esther B ^b   Singh, Bharat ^a   Jensen, Craig M ^b   Goldman, Alan S ^a  

^a RUTGERS UNIVERSITY   (United States)

^b UNIVERSITY OF HAWAII   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALKANE; ALKENE DERIVATIVE;

ARTICLE; CATALYSIS; CHEMICAL BOND; CHEMICAL MODIFICATION; CHEMICAL STRUCTURE; ISOMERISM; REACTION ANALYSIS; STEREOCHEMISTRY; SYNTHESIS;

EID: 0033611987     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja983460p     Document Type: Article

References (25)

1. Lappin, G. R.; Nemec, L. H.; Sauer, J. D.; Wagner, J. D. In Kirk-Othmer Encyclopedia of Chemical Technology, 4th ed.; Kroschwitz, J. I., Howe-Grant, M., Eds.; Wiley-Interscience: New York, 1996; Vol. 17; pp 839-858.
2. Behr, A. In Ullmann's Encyclopedia of Industrial Chemistry, 5th ed.; Elvers, B., Hawkins, S., Russey, W., Eds.; VCH Verlagsgesellschaft: Weinheim, 1989; Vol. A13; pp 240-251.
3. Despite the much greater bond strengths of primary vs secondary C-H bonds of n-alkanes, catalysts have been reported capable of oxidation of the former. However, to our knowledge, selectivity for primary oxidation is at best only approximately 1:1 on a per bond basis, in contrast with that of the present work (> 20:1). For some lead references see: (a) Sen, A. Acc. Chem. Res. 1998, 31, 550-557. (b) Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879-2932. (c) Metalloporphyrins in Catalytic Oxidations; Sheldon, R. A., Ed.; Marcel Dekker: New York, 1994.
4. Despite the much greater bond strengths of primary vs secondary C-H bonds of n-alkanes, catalysts have been reported capable of oxidation of the former. However, to our knowledge, selectivity for primary oxidation is at best only approximately 1:1 on a per bond basis, in contrast with that of the present work (> 20:1). For some lead references see: (a) Sen, A. Acc. Chem. Res. 1998, 31, 550-557. (b) Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879-2932. (c) Metalloporphyrins in Catalytic Oxidations; Sheldon, R. A., Ed.; Marcel Dekker: New York, 1994.
5. Despite the much greater bond strengths of primary vs secondary C-H bonds of n-alkanes, catalysts have been reported capable of oxidation of the former. However, to our knowledge, selectivity for primary oxidation is at best only approximately 1:1 on a per bond basis, in contrast with that of the present work (> 20:1). For some lead references see: (a) Sen, A. Acc. Chem. Res. 1998, 31, 550-557. (b) Shilov, A. E.; Shul'pin, G. B. Chem. Rev. 1997, 97, 2879-2932. (c) Metalloporphyrins in Catalytic Oxidations; Sheldon, R. A., Ed.; Marcel Dekker: New York, 1994.
6. A photochemical system first reported by Tanaka has been modified to give efficient and regioselective carbonylation of the terminal position of n-alkanes: (a) Sakakura, T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M. J. Am. Chem. Soc. 1990, 112, 7221-7229. (b) Rosini, G. P.; Zhu, K.; Goldman, A. S. J. Organomet. Chem. 1995, 504, 115-121.
7. A photochemical system first reported by Tanaka has been modified to give efficient and regioselective carbonylation of the terminal position of n-alkanes: (a) Sakakura, T.; Sodeyama, T.; Sasaki, K.; Wada, K.; Tanaka, M. J. Am. Chem. Soc. 1990, 112, 7221-7229. (b) Rosini, G. P.; Zhu, K.; Goldman, A. S. J. Organomet. Chem. 1995, 504, 115-121.
8. (a) Janowicz, A. H.; Bergman, R. G. J. Am. Chem. Soc. 1982, 104, 352-354.
9. (b) Hoyano, J. K.; Graham, W. A. G. J. Am. Chem. Soc. 1982, 104, 3723.
10. (a) Arndtsen, B. A.; Bergman, R. G.; Mobley, T. A.; Peterson, T. H. Acc. Chem. Res. 1995, 28, 154-162.
11. (b) Jones, W. D.; Feher, F. J. Acc. Chem. Res. 1989, 22, 91-100.
12. (c) Harper, T. G. P.; Desrosiers, P. J.; Flood, T. C. Organometallics 1990, 9, 2523-2528.
13. For excellent discussions of the kinetic and thermodynamic selectivity exhibited by transition metal complexes toward C-H bonds, particularly in terms of factors other than steric, see the following and references therein: (a) Bennett, J. L.; Vaid, T. P.; Wolczanski, P. T. Inorg. Chim. Acta 1998, 270(1-2), 414-423 (b) Wick, D. D.; Jones, W. D. Organometallics 1999, 18, 495-505.
14. For excellent discussions of the kinetic and thermodynamic selectivity exhibited by transition metal complexes toward C-H bonds, particularly in terms of factors other than steric, see the following and references therein: (a) Bennett, J. L.; Vaid, T. P.; Wolczanski, P. T. Inorg. Chim. Acta 1998, 270(1-2), 414-423 (b) Wick, D. D.; Jones, W. D. Organometallics 1999, 18, 495-505.
15. (a) Baudry, D.; Ephritikine, M.; Felkin, H.; Holmes-Smith, R. J. Chem. Soc., Chem. Commun. 1983, 788-789.
16. (b) Felkin, H.; Fillebeen-Khan, T.; Holmes-Smith, R.; Lin, Y. Tetrahedron Lett. 1985, 26, 1999-2000.
17. (a) Burk, M. J.; Crabtree, R. H.; Parnell, C. P.; Uriarte, R. J. Organometallics 1984, 3, 816-817.
18. (b) Burk, M. J.; Crabtree, R. H. J. Am. Chem. Soc. 1987, 109, 8025-8032.
19. (a) Gupta, M.; Hagen, C.; Flesher, R. J.; Kaska, W. C.; Jensen, C. M. Chem. Commun. 1996, 2083-2084.
20. (b) Gupta, M.; Hagen, C.; Kaska, W. C.; Cramer, R. E.; Jensen, C. M. J. Am. Chem. Soc. 1997, 119, 840-841.
21. Hagen, C.; Gupta, M.; Kaska, W. C.; Jensen, C. M. Paper INOR 221, presented at the 213th American Chemical Society National Meeting, San Francisco, CA, April 13, 1997.
22. 10
23. Rybtchinski, B.; Vigalok, A.; Bendavid, Y.; Milstein, D. Organometallics 1997, 16, 3786-3793.
24. Concentrations were determined by GC (see ref 10). In all cases the measured concentration of hydrogenated sacrificial acceptor was within 20% of ([octenes] + 2 × [dienes]).
25. 4).