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Previously we have shown that interaction of the simplest N,N-dimethylbenzylaminate palladacycle with chlorine dioxide results in the formation of a 3-chlorinated palladacycle instead of the expected hydroxylation product. It was reasonably to assume that this transformation includes the Pd–C bond chlorination of the CN-palladacycle followed by repeated cyclopalladation of ortho-Cl-substituted ligand thus formed. This guess was verified stereochemically using optically active palladacycle (R)-1 derived from prochiral benzylamine ligand. At preliminary stage this reaction has been conducted on the dimer rac-1. The formation of the intermediate Pd-coordinated 2-chlorinated amine (R)-I/II and its further ortho-palladation at unsubstituted phenyl ring was unambiguously confirmed by X-ray study of the PPh3 adduct rac-2. The most important evidences in support of the proposed mechanistic pathway are: i) inversion of the α-C*-stereocentre configuration at the first stage of this process [from (R)-1 to (S)-2] (evident from opposite sign of the specific rotation), and ii) its complete racemization at the second step of the prochiral 2,2'-dichlorinated benzylamine cyclopalladation [from (S)-2 to rac-3] ([α]D = 0).