A significant effect of anion binding ureas on the product ratio in the palladium(II)-catalyzed hydrocarbonylation of alkenes

Abstract

Hydrogen bonding of urea derivatives to the anionic ligands X of (dppp)PdX₂ catalysts significantly increases the hydroacylation of cyclopentene relative to the hydroformylation, most probably due to a decreased coordination strength of the anionic ligands.

References

1. H. H. Brintzinger, D. Fisher, R. Mülhaupt, B. Rieger and R. M. Waymouth, Angew. Chem., Int. Ed. Engl., 1995, 34, 1143; P. Margl, L. Deng and T. Ziegler, Organometallics, 1998, 17, 933.
2. E. Drent, Eur. Pat. Appl. 121,965 A2, 1984; E. Drent, J. A. M. van Broekhoven and M. J. Doyle, J. Organomet. Chem., 1991, 417, 235; A. Sen, Adv. Polym. Sci., 1986, 73/74, 125.
3. E. Drent and P. H. M. Budzelaar, Chem. Rev., 1996, 96, 663; C. Pisano and G. Consiglio, Gazz. Chim. Ital., 1994, 124, 393.
4. A. Yamamoto, J. Organomet. Chem., 1995, 500, 337.
5. E. Drent, Pure Appl. Chem., 1990, 62, 661.
6. L. K. Johnson, C. M. Killian and M. Brookhart, J. Am. Chem. Soc., 1995, 117, 6415.
7. F. Agbossou, J. F. Carpentier and A. Mortreux, Chem. Rev., 1995, 95, 2485.
8. S. Valiyaveettil, J. F. J. Engbersen, W. Verboom and D. N. Reinhoudt, Angew. Chem., Int. Ed. Engl., 1993, 32, 900.
9. J. Scheerder, J. P. M. van Duynhoven, J. F. J. Engbersen and D. N. Reinhoudt, Angew. Chem., Int. Ed. Engl., 1996, 35, 1090.
10. D. M. Rudkevich, Z. Brzozka, M. J. Palys, W. P. R. V. Stauthamer, G. J. van Hummel, S. M. Franken, S. Harkema, J. F. J. Engbersen and D. N. Reinhoudt, J. Am. Chem. Soc., 1994, 116, 4341.
11. M. M. G. Antonisse, B. H. M. Snellink-Ruël, J. F. J. Engbersen and D. N. Reinhoudt, J. Chem Soc., Perkin Trans. 2, 1998, 773.
12. V. van Axel Castelli, R. Cacciapaglia, G. Chiosis, F. C. J. M. van Veggel, L. Mandolini and D. N. Reinhoudt, Inorg. Chim. Acta, 1996, 246, 1.
13. Ureas are known to bind to a variety of (delocalized) anions via hydrogen bonding E. Fan, S. A. Van Arman, S. Kincaid and A. D. Hamilton, J. Am. Chem. Soc., 1993, 115, 369.
14. van Koten, Angew. Chem., Int. Ed. Engl., 1996, 35, 1959; K. Biradha and G. R. Desiraju, Organometallics, 1996, 15, 1284; E. S. Shubina, N. V. Belkova and L. M. Epstein, J. Organomet. Chem., 1997, 536–537, 17; F. Grepioni, G. Cojazzi, S. M. Draper, N. Scully and D. Braga, Organometallics, 1998, 17, 296.
15. The influence of thiourea on the palladium catalyzed reaction of terminal alkynes has been reported. However, this effect is attributed to coordination of the thiocarbonyl moiety to the Pd center not to hydrogen bonding B. Gabriele, G. Salerno, M. Costa and G. P. Chiusoli, J. Organomet. Chem., 1995, 503, 21.
16. G. P. C. M. Dekker, C. J. Elsevier, K. Vrieze, P. W. N. M. van Leeuwen and C. F. Roobeek, J. Organomet. Chem., 1992, 430, 357.
17. C. S. Wilcox, E. Kim, D. Romano, L. H. Kuo, A. L. Burt and D. P. Curran, Tetrahedron, 1995, 51, 621.
18. S. Nishizawa, P. Bühlmann, K. P. Xiao and Y. Umezawa, Anal. Chim. Acta, 1998, 358, 35.
19. Chloroform has approximately the same solvation strength as anisole. Y. Marcus, Ion Solvation, Wiley, New York, 1985.