Heterogeneous transfer hydrogenation involves pairwise hydrogen transfer from the same position of two molecules of formic acid

Abstract

Using the reduction of an alkyne to cis-alkene as a hydrogen trap, differentially deuterium labelled formic acid is shown to deliver a pair of hydrogen atoms either from the formyl or the carboxy position, which suggests that palladium diformate is a key intermediate in heterogeneous transfer hydrogenation.

References

1. A. Fujii, S. Hashiguchi, N. Uematsu, T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1996, 118, 2521.
2. N. Uematsu, A. Fujii, S. Hashiguchi, T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1996, 118, 4916.
3. K. Matsumura, S. Hashiguchi, T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1997, 119, 8738.
4. R. Noyori and S. Hashiguchi, Acc. Chem. Res., 1997, 30, 97.
5. E. T. Sundquist, Science, 1993, 259, 934.
6. P. G. Jessop, I. Takao and R. Noyori, Nature, 1994, 368, 231.
7. P. G. Jessop, I. Takao and R. Noyori, Chem. Rev., 1995, 95, 259.
8. W. Leitner, Angew. Chem., Int. Ed. Engl., 1995, 34, 2207.
9. W. Leitner, J. M. Brown and H. Brunner, J. Am. Chem. Soc., 1993, 115, 152.
10. P. G. Jessop, Y. Hsiao, T. Ikariya and R. Noyori, J. Am. Chem. Soc., 1996, 118, 344.
11. F. Hutschka, A. Dedieu, M. Eichberger, R. Fornika and W. Leitner, J. Am. Chem. Soc., 1997, 119, 4432.
12. J. Tsai and K. M. Nicholas, J. Am. Chem. Soc., 1992, 114, 5117.
13. E. Lindner, B. Keppeler and P. Wegner, Inorg. Chim. Acta, 1997, 258, 97.
14. J. Halpern, Science, 1982, 217, 401.
15. J. Yu and J. B. Spencer, J. Am. Chem. Soc., 1997, 119, 5257.
16. J. Yu and J. B. Spencer, J. Org. Chem., 1997, 62, 8618.
17. J. A. Osborn, F. H. Jardine, J. F. Young and G. Wilkinson, J. Chem. Soc. (A), 1996, 1711.
18. S. M. Morehouse, A. R. Powell, J. P. Heffer, T. A. Stephenson and G. Wilkinson, Chem. Ind., 1964, 544.
19. D. Mootz and R. Seidel, Acta Crystallogr., Sect. C, 1987, 43, 1218.
20. H. Suzuki, T. Ikegami, Y. Matano and N. Azuma, J. Chem. Soc., Perkin Trans. 1, 1993, 2411.
21. M. K. Whittlesey, R. N. Perutz and M. H. Moore, Organometallics, 1996, 15, 5166.