Abstract
The catalytic activity and stereoselectivity of Rh(I) complexes with C 2-symmetric chiral diamines, (4S,5S)-3,4-isopropylidenedioxy-1,4-butanediamine and (4S,5S)-N,N,N',N'-tetramethyl-3,4-isopropylidenedioxy-1,4-butanediamine [skeletal analogs of 2,3-dihydroxy-2,3-O-isopropylidene-1,4-bis(diphenylphosphino)butane (DIOP)], were studied in hydrogen transfer from 2-propanol to acetophenone in the presence of KOH or t-BuOK. The product, (S)-(-)-2-phenylethanol, was thus obtained with an optical yield of 67%. Covalent chloride rhodium complexes with the above ligands give rise to the same stereoisomer, whereas the opposite stereoselectivity is observed under catalysis by cationic trifluoromethanesulfonate rhodium(I) complexes. X-Ray phase analysis showed formation of nanosize particles in the precipitate of metallic rhodium.
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REFERENCES
Botteghi, C., Chelucci, G., Chessa, G., Delogu, G., Gladiali, S., and Soccolini, F. J. Organomet. Chem., 1986, vol. 304, p. 217.
Gladiali, S., Chelucci, G., Soccolini, F., Delogu, G., and Chessa, G., J. Organomet. Chem., 1989, vol. 370, p. 285.
Pavlov, V.A., Vinogradov, M.G., Starodubtseva, E.V., Chel'tsova, G.V., Ferapontov, V.A., Malyshev, O.R., and Kheis, G.L., Izv. Ross. Akad. Nauk, Ser. Khim., 2001, p. 704.
Zassinovich, G. and Mestroni, G., J. Mol. Catal., 1987, vol. 42, p. 81.
Maillard, D., Pozzi, G., Quici, S., and Sinou, D., Tetrahedron, 2002, vol. 58, p. 3971.
Noyori, R. and Hashiguchi, S., Acc. Chem. Res., 1997, vol. 30, p. 97.
Touchard, F., Bernard, M., Fache, F., Delbecq, F., Guiral, V., Sautet, P., and Lemaire, M., J. Organomet. Chem., 1998, vol. 567, p. 133.
Touchard, F., Bernard, M., Fache, F., and Lemaire, M., J. Mol. Catal., 1999, vol. 140, p. 1.
Nindakova, L.O., Shainyan, B.A., and Albanov, A.I., Izv. Ross. Akad. Nauk, Ser. Khim., 2001, p. 1772.
Shainyan, B.A., Ustinov, M.V., and Nindakova, L.O., Russ. J. Org. Chem., 2001, vol. 37, p. 1757.
Shainyan, B.A., Ustinov, M.V., Bel'skii, V.K., and Nindakova, L.O., Russ. J. Org. Chem., 2002, vol. 38, p. 104.
Shainyan, B.A., Nindakova, L.O., Ustinov, M.V., Chipanina, N.N., and Sherstyannikova, L.V., Russ. J. Org. Chem., 2002, vol. 38, p. 1802.
Uson, R., Oro, L.A., Claver, C., and Garralda, M.A., J. Organomet. Chem., 1976, vol. 105, p. 365.
Garralda, M.A. and Ibarlucea, L., J. Organomet. Chem., 1986, vol. 311, p. 225.
Palmer, M.J. and Wills, M., Tetrahedron: Asymmetry, 1999, vol. 10, p. 2045.
Powder Diffraction File, Philadelphia: ICPDS, 1977, vol. 5, no. 0685.
Lipson, H. and Steeple, H., Interpretation of X-Ray Powder Diffraction Patterns, London: Macmillan, 1970.
Bonemann, H. and Braun, G.A., Angew. Chem. Int. Ed., 1996, vol. 35, p. 1992.
Seebach, D., Kalinowski, H.O., Bastini, B., Crass, G., Daum, H., Doerr, H., DuPreez, N.P., Ehrig, V., and Langer, W., Helv. Chim. Acta, 1977, vol. 60, p. 301.
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Nindakova, L.O., Shainyan, B.A. & Belonogova, L.N. Catalytic Hydrogenation of Acetophenone with Hydrogen Transfer over Chiral Diamine Rhodium(I) Complexes. Russian Journal of Organic Chemistry 39, 1484–1488 (2003). https://doi.org/10.1023/B:RUJO.0000010566.99408.65
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DOI: https://doi.org/10.1023/B:RUJO.0000010566.99408.65