Synthesis, Characterization Of N-donor Ligands Bearing 2-furfuryl Moiety And Their Palladation Reactions

This thesis summarized in detail the progress of palladation reactions of N-donor ligands particularly for those bearing 2-furfuryl group. Based on the previous studies, three series, eight furfurylideneamines and two series, total five ter-amines were synthesized from the starting material furfural. Their palladation reactions and characterizations were discussed.1. Synthesis, characterization of imines and their palladated complexesCondensation of furfural with substituted benzylamines, chiral benzylamines and anilines in methanol or water at room temperature resulted in aldimines. Treatment of these imines with sodium tetrachloropalladate in methanol and dichloromethane led to the corresponding palladated complexes.2. Synthesis,characterization of [(N-methyl-N-2-furfuryl)-(α)-methylbenzyl]amines and their cyclopalladated complexesReduction of the imines resulted from by furfural and substituted benzyl- amines, chiral benzylamines with sodium borohydride in methanol produced quantitative sec-amines. Reductive methylation of these sec-amines with sodiumcyanoborohydride, formaldehyde in acetonitrile and acetic acid gave out the corresponding ter-amines. Cyclopalladation of these amines with sodium tetra- chloropalladate in methanol and dichloromethane led to cyclopalladated complexesThe imines and ter-amines as well as their palladated complexes were characterized by elemental analysis, IR and 1HNMR. The structures of three of the palladated complexes were confirmed by X-Ray single crystal diffraction. The possible mechanism for the formation of cyclopalladated complexes was discussed.