Stereospecific co-crystallization of reactant and palladium complex in the resolution of stilbendiamine using N*-chiral ortho-palladated matrix

Author:

Dunina V.V,Kuz'mina L.G,Parfyonov A.G,Grishin Yu.K

Publisher

Elsevier BV

Subject

Inorganic Chemistry,Organic Chemistry,Physical and Theoretical Chemistry,Catalysis

Reference12 articles.

1. Review: Pietrusiewicz, K. M., Zablocka, M., Chem. Rev. 1994, 94, 1375–1411.

2. Examples of recent references: Chooi, Y. M., Ranford, J. D., Leung, P.-H., Mok, K. F., Tetrahedron: Asymmetry, 1994, 5, 1805–1814; Lim, C.-C., Leung, P.-H., Sim, K. Y., Tetrahedron: Asymmetry, 1994, 5, 1883–1886; Hockless, D. C. R., Mayadunne, R. C., Wild, S. B., Tetrahedron: Asymmetry, 1995, 6, 3031–3037; Dunina, V. V., Golovan', E. B., Tetrahedron: Asymmetry, 1995, 6, 2747; Pabel, M., Willis, A. C., Wild, S. B., Inorg. Chem., 1996, 35, 1244–1249.

3. Leung, P.-H., McLaughlin, G. M., Martin, J. W. L., Wild, S. B., Inorg. Chem., 1986, 25, 3392; Dai, L., Zhou, Zh., Zhang, Y., Ni, Ch., Zhang, Zh., Zhou, Y., J. Chem. Soc., Chem. Commun., 1987, 1760–1762; Wang, X. Ch., Cui, Y. X., Mak, Th. C. W., Wong, H. C., J. Chem. Soc., Chem. Commun., 1990, 167–169; Chelucci, G., Cabras, M. A., Saba, A., Sechi, A., Tetrahedron: Asymmetry, 1996, 7, 1027–1032.

4. For (SCRN,SS)-2a: m.p. (dec) 204–206°C, [α]D20 −34.3 (c 1.5, MeOH). Anal. calcd: C, 56.18; H, 6.41; N, 7.86 for C25H32ClN3Pd·H2O. Found: C, 56.01; H, 6.14; N, 7.75. Diastereomeric purity (88% de) was determined by 1H NMR using the integral intensity of the Me groups of the NPri substituent.

5. The 1H NMR spectra of the starting mixture of dimer (SCRN)-1 and racemic Stien in a 1:4 molar ratio contains two sets of signals from the two diastereomers 2a,b in nearly a 1:1 ratio and the signals of free diamine. The absence of stereoselectivity in their complexation seems to be a result of the low efficiency of steric interactions between the benzylaminate palladacycle and the primary amino groups of the diamine (cf. findings of Leung et al.6); it is likely that the disruption of the agostic interaction iso-Pr…Pd in a polar medium may decrease the conformational stability and ability to chiral recognition of palladacycle as well.

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