Orthopalladated triaryl phosphite complexes as highly active catalysts in biaryl coupling reactions

Abstract

Orthopalladation of inexpensive, commercially available tris(2,4-di-tert-butylphenyl) phosphite gives a dimeric complex 3 which proves to be an extremely active catalyst in biaryl coupling reactions, giving unprecedented turnover numbers of up to 1000000 [mol product (mol Pd)^–1] and turnover frequencies of nearly 900000 [mol product (mol Pd)^–1 h^–1] in the Suzuki reaction and turnover numbers of up to 830000 in the Stille reaction.

References

1. K. Nozaki, N. Sakai, T. Nanno, T. Higashijima, S. Mano, T. Horiuchi and H. Takaya, J. Am. Chem. Soc., 1997, 119, 4413 and references cited therein A. van Rooy, E. N. Orij, P. C. J. Kamer, F. van den Aardweg and P. W. M. N. van Leeuwen, J. Chem. Soc., Chem. Commun., 1991, 1096; A. Polo, C. Claver, S. Castillón, A. Ruiz, J. C. Bayon, J. Real, C. Mealli and D. Massi, Organometallics, 1992, 11, 3525; N. Sakai, K. Nozaki and H. Takaya, J. Chem. Soc., Chem. Commun., 1994, 395.
2. T. Horiuchi, E. Shirakawa, K. Nozaki and H. Takaya, Tetrahedron: Asymmetry, 1997, 8, 57.
3. K. Nozaki, N. Sato and H. Takaya, J. Am. Chem. Soc., 1995, 117, 9911.
4. (a) R. B. Bedford, P. A. Chaloner and P. B. Hitchcock, J. Chem. Soc., Chem. Commun., 1995, 2049; (b) R. B. Bedford, S. Castillon, P. A. Chaloner, C. Claver, E. Fernandez, P. B. Hitchcock and A. Ruiz, Organometallics, 1996, 15, 3990.
5. L. N. Lewis, J. Am. Chem. Soc., 1986, 108, 743; L. N. Lewis, Inorg. Chem., 1985, 24, 4433.
6. L. N. Lewis and J. F. Smith, J. Am. Chem. Soc., 1986, 108, 2728.
7. M. Beller, H. Fischer, W. A. Herrmann, K. Öfele and C. Brossmer, Angew. Chem. Int. Ed. Engl., 1995, 34, 1848.
8. J. C. Anderson, H. Namli and C. A. Roberts, Tetrahedron, 1997, 53, 15 123; J. C. Anderson and H. Namli, Synlett, 1995, 765.
9. J. Louie and J. F. Hartwig, Angew. Chem., Int. Ed. Engl., 1996, 35, 2359.
10. B. L. Shaw, New J. Chem., 1998, 77; B. L. Shaw, S. D. Perera and E. A. Staley, Chem. Commun., 1998, 1361.