Selective catalytic C-H alkylation of alkenes with alcohols

Science

Volumn 333, Issue 6049, 2011, Pages 1613-1616

  Lee, Dong Hwan ^a   Kwon, Ki Hyeok ^a   Yi, Chae S ^a  

^a Marquette University   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

ALCOHOL DERIVATIVE; ALKENE; CARBON; CARBONYL DERIVATIVE; HYDROGEN; RUTHENIUM COMPLEX;

ALCOHOL; ALKENE; CATALYSIS; CATION; CHEMICAL BONDING; COMPLEXATION; ELECTROCHEMISTRY; INDUSTRIAL PRODUCTION; ORGANOMETALLIC COMPOUND; POLARIZATION; REACTION KINETICS; RUTHENIUM; TEMPERATURE PROFILE;

ALKYLATION; ARTICLE; CATALYSIS; CHEMICAL STRUCTURE; ELECTROPHILICITY; FRIEDEL CRAFTS REACTION; POLARIZATION; PRIORITY JOURNAL; TEMPERATURE MEASUREMENT; WATER LOSS;

EID: 80052945833     PISSN: 00368075     EISSN: 10959203     Source Type: Journal    
DOI: 10.1126/science.1208839     Document Type: Article

References (33)

1. G. A. Olah, A. Molnár, Hydrocarbon Chemistry (Wiley, New York, 2003).
2. R. F. Heck, Acc. Chem. Res. 12, 146 (1979).
3. J.-Q. Yu, Z. Shi, Eds., C-H Activation (Springer, New York, 2010).
4. S. Murai et al., Nature 366, 529 (1993).
5. D. A. Colby, R. G. Bergman, J. A. Ellman, Chem. Rev. 110, 624 (2010).
6. C. S. Yeung, V. M. Dong, Chem. Rev. 111, 1215 (2011).
7. C.-J. Li, Acc. Chem. Res. 42, 335 (2009).
8. D. R. Stuart, K. Fagnou, Science 316, 1172 (2007).
9. D.-H. Wang, K. M. Engle, B.-F. Shi, J.-Q. Yu, Science 327, 315 (2010); 10.1126/science.1182512.
10. M. B. Smith, J. March, March's Advanced Organic Chemistry (Wiley, New York, 2001).
11. C. S. Yi, D. W. Lee, Organometallics 28, 4266 (2009).
12. C. S. Yi, D. W. Lee, Organometallics 29, 1883 (2010).
13. G. E. Dobereiner, R. H. Crabtree, Chem. Rev. 110, 681 (2010).
14. D. V. McGrath, R. H. Grubbs, Organometallics 13, 224 (1994).
15. F. C. Courchay, J. C. Sworen, I. Ghiviriga, K. A. Abboud, K. B. Wagener, Organometallics 25, 6074 (2006).
16. D. W. Lee, C. S. Yi, Organometallics 29, 3413 (2010).
17. M. Karplus, J. Chem. Phys. 30, 11 (1959).
18. The regioselective deuterium exchange on the C-2 carbon of indene is most consistent with the vinyl C-H activation mechanism. The selective deuterium incorporation on the C-1 and C-3 carbons of indan can readily be explained from regioselective insertion of indene to Ru-D, followed by reductive elimination with the hydride formed from the vinyl C-H activation of another indene molecule. Due to steric hindrance from the arene hydrogen, metalation and insertion of the Ru atom are expected to be favored at the C-2 carbon of indene. Previously, we also observed the formation free benzene molecule in the reactions catalyzed by 1 (12, 16).
19. R. M. Roberts, A. A. Khalaf, Friedel-Crafts Alkylation Chemistry: A Century of Discovery (Dekker, New York, 1984).
20. G. A. Olah, R. Krishnamurti, G. K. S. Prakash, in Comprehensive Organic Synthesis, B. M. Trost, I. Fleming, Eds. (Pergamon, New York, 1991), vol. 3, chap. 1.8.
21. Z.-Q. Liu et al., Org. Lett. 13, 2208 (2011).
22. D. E. Frantz, D. A. Singleton, J. P. Snyder, J. Am. Chem. Soc. 119, 3383 (1997).
23. R. Gao, C. S. Yi, J. Org. Chem. 75, 3144 (2010).
24. F. Kakiuchi, S. Murai, Acc. Chem. Res. 35, 826 (2002).
25. Transition metal-vinyl complexes have been proposed to be a key intermediate in C-H bond activation chemistry. For representative examples, see (32, 33).
26. The formation of a free benzene molecule (2%) is detected after heating the reaction mixture at 70°C for 15 min using 5 mol % of 1. Previously, we observed similar results in the reactions catalyzed by 1 (12, 16).
27. Y. Feng et al., J. Am. Chem. Soc. 127, 14174 (2005).
28. T. Matsumoto, Y. Nakaya, N. Itakura, K. Tatsumi, J. Am. Chem. Soc. 130, 2458 (2008).
29. D. Rondon, B. Chaudret, X. D. He, D. Labroue, J. Am. Chem. Soc. 113, 5671 (1991).
30. D. B. Grotjahn, H. C. Lo, Organometallics 15, 2860 (1996).
31. S. Ueno, E. Mizushima, N. Chatani, F. Kakiuchi, J. Am. Chem. Soc. 128, 16516 (2006).
32. P. O. Stoutland, R. G. Bergman, J. Am. Chem. Soc. 107, 4581 (1985).
33. K. B. Renkema, Y. V. Kissin, A. S. Goldman, J. Am. Chem. Soc. 125, 7770 (2003).