Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one


Synthesized and characterized new chiral palladium complexes, some of which contain asymmetric donor nitrogen atom. Nitrogen-containing derivatives (+) - and (-)-2α-hydroxypinan-3-one- (1R,2R,5R)-3-(benzylimino)-2,6,6-trimethylbicy- clo[3.1.1]heptane-2-ol (HL1), (1S,2S,3S,5S)-3- (benzylamino)-2,6, 6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL2), (1R,2R,5R)-3-((S)-α-methyl- benzylimino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL3), (1R,2R,3R,5R)-3-((S)-α-methyl- benzylamino)-2,6,6-trimethylbicyclo[3.1.1]- heptane-2-ol (HL4) -were studied as optically active ligands.

Share and Cite:

Zalevskaya, O. , Gur'eva, Y. , Frolova, L. , Alekseev, I. and Kutchin, A. (2010) Chiral palladium complexes based on derivatives of benzylamine and 2α-hydroxypinan-3-one. Natural Science, 2, 1189-1194. doi: 10.4236/ns.2010.211147.

Conflicts of Interest

The authors declare no conflicts of interest.


[1] Dupont, J., Consorti, C.S. and Spencer, J. (2005) The potential of palladacycles: More than just precatalysts. Chemical Reviews, 105, 2527-2571.
[2] Loh, S.K., Vittal, J.J. and Leung, P.H. (1998) 1-Methyl-2-vinylpyrrole and 1-phenyl-3,4-dimethylphosphole: Their coordination chemistries and reactivities in a chiral palladium complex promoted asymmetric Diels-Alder reaction. Tetrahedron: Asymmetry, 9, 423- 428.
[3] Ding, Y., Li, Y., Zhang, Y., Pullarkat, S.A. and Leung, P.H. (2008) Design, synthesis and stereochemical evaluation of a novel chiral amine-palladacycle. European Journal of Inorganic Chemistry, 2008, 1880-1891.
[4] Gugger, P.A.,Willis, A.C., Wild, S.B., Heath, G.A., Webster, R.D. and Nelson, J.H. (2002) Enantioselective synthesis of a conformationally rigid, sterically encumbered, 2-arsino-7-phosphanorbornene. The Journal of Organometallic Chemistry, 643, 136-153.
[5] Zhao, V. I. (1999) Insertion reaction between planar chiral cyclopalladated derivatives of ferrocene and diphenylacetylene. The Journal of Organometallic Chemistry, 574, 311-317.
[6] Sokolov, V.I. (1995) Optically active organometallic compounds (a personal account from the inside). The Journal of Organometallic Chemistry, 500, 299- 306.
[7] Spencer, J. and Pfeffer, M. (1995) The fate of the stereogenic centre linked to palladium upon reaction with an alkyne. Tetrahedron: Asymmetry, 6, 419-426.
[8] Hollis, T.K. and Overman, L.E. (1997) Cyclopalladated ferrocenyl amines as enantioselective catalysts for the rearrangement of allylic imidates to allylic amides. Tetrahedron Letters, 38, 8837-8840.
[9] Chahen, L., Therrien, B. and Suss-Fink, G. (2007) Square-planar diacetatopalladium complexes with trans- configured secondary amine ligands that avoid orthometalation: ligand synthesis, coordination, molecular structure and catalytic potential for suzuki cross-coupling reactions. European Journal of Inorganic Chemistry, 2007, 5045-5051.
[10] Zalevskaya, O.A., Vorob’eva, E.G., Dvornikova, I.A. and Kuchin, A.V. (2008) Palladium complexes based on optically active terpene derivatives of ethylenediamine. Russian Journal of Coordination Chemistry, 34, 855- 857.
[11] Overman, L.E. and Remarchuk, T.P. (2000) Catalytic asymmetric intramolecular aminopalladation: enantioselective synthesis of vinyl-substituted 2-oxazoli dinones, 2-imidazolidinones, and 2-pyrrolidinones. Journal of American Chemical Society, 124, 12-13.
[12] Kirsch, S.F. and Overman, L.E. (2005) Catalytic asymmetric synthesis of chiral allylic esters. Journal of American Chemical Society, 127, 2866-2867.
[13] Levrat, F., Stoeckli-Evans, H. and Engel, N. (2002) Enantiomeric excess determination of α-amino acids by 19F NMR spectroscopy of their N,N-dimethyl-(2,2,2- trifluoro-1-phenylethyl)amine-C,N)palladium complexes. Tetrahedron: Asymmetry, 13, 2335-2344.
[14] Dunina, V. V., Kuz'mina, L. G., Kazakova, M.Y., Grishin, Y.K., Veits, Y.A. and Kazakova, E.I. (1997) Ortho-palladated α-phenylalkylamines for enantiomeric purity determination of monodentate P*-chiral phosphines, Tetrahedron: Asymmetry, 8, 2537-2545.
[15] Albert, J., Granell, J., Muller, G., Sainz, D., Font-Bardia, M. and Solans, X. (1995) Chiral Cyclopalladated compounds for enantiomeric purities of functionalized phosphines by means of multinuclear NMR. Tetrahedron: Asymmetry, 6, 325.
[16] Ding, Y., Chiang, M., Pullarkat, S.A., Li, Y. and Leung, P.H. (2009) Synthesis, coordination characteristics, conformational behavior and bond reactivity studies of a novel chiral phosphapalladacycle complex. Organome- tallics, 28, 4358-4370.
[17] Albert, J., Cadena, J.M., Delgado, S. and Granell, J. (2000) Synthesis and resolution of a new P-chiral hydroxy phosphine. The Journal of Organometallic Chemistry, 603, 235-239.
[18] Dunina, V.V., Kuz'mina, L.G., Rubina, M.Y., Grishin, Y.K., Veits, Y.A. and Kazakova, E.I. (1999) A resolution of the monodentate P*-chiral phosphine PBU(t)C6H4Br-4 and its NMR-deduced absolute configuration. Tetrahedron: Asymmetry, 10, 1483-1497.
[19] Gur'eva, Y.A., Zalevskaya, O.A., Frolova, L.L., Alexeev, I.N. and Kutchin, A.V. Chiral imines and amines on the basis of 2α-hydroxypinan-3-one. Chemistry of Natural Compounds, in press.
[20] Cope, A.C. and Siekman, R.W. (1965) Formation of covalent bonds from platinum or palladium to carbon by direct substitution. Journal of American Chemical Society, 87, 3272-3273.

Copyright © 2021 by authors and Scientific Research Publishing Inc.

Creative Commons License

This work and the related PDF file are licensed under a Creative Commons Attribution 4.0 International License.