ИСТИНА

Primary objectives and scope of the project. In this project we planned to study a possibility to increase the ability of cyclopalladated compounds to chiral recognition due to the asymmetry of nitrogen donor atom.

FIRST YEAR: In the initial stage of project performance a series of new N*-chiral cyclopalladated complexes of tertiary and secondary benzylamines bearing bulky alpha-C- or N-substituent in enantiopure or racemic state were obtained by direct intramolecular ortho-palladation and completely characterized by IR, NMR 1H, 31P{1H}, CD, mass-spectroscopy and X-ray data1. Coordinate intermediates of palladation process were isolated and characterized as well. The competition between the processes of activation of (sp3)C-H and (sp2)C-H bonds in secondary N-methyl-alpha-tert-butylbenzylamine was discovered; the conditions of regioselective formation of one of regioisomers was found. A very rare example of (sp3)C-C(sp3) bond activation in the same secondary amine by Pd(II) under very mild condition was discovered; as the result the formation of ortho-palladated N-methylbenzylideneimine was established2. SECOND YEAR: For the first time the systematic investigation of ability of CPC to chiral recognition was performed using the complexation with monodentate P*-chiral phosphine as a model process. The methodology of determination of complexation diastereoselectivity by low-temperature NMR 31P spectroscopy in the therms of equilibrium constants was developed. It was disclosed a very high contribution of N*-stereocentre into the enantiomers discrimination in the case of the derivative of secondary amine bearing one bulky N-substituent.