Studies On Cyclometallations Of Tert-Ferrocenylbenzylamines And Their Catalysis In Carbon-carbon Cross Coupling Reaction

This thesis summarized in detail the progress of cyclometallation reactions of N-donor ligands particularly for the ferrocene derivatives. Based on the previous progress, three series, total ten tertiary ferrocenylamines were synthesized from the starting material ferrocene. Their cyclometallation reactions (M = Hg, Pd, Pt) and the catalysis in the carbon-carbon bond cross coupling reactions for the cyclopalladated complexes as well as the antitumor activity of cycloplatinated complexes were discussed.1. Synthesis, characterization of [{(N-methyl-N-p-R-benzyl)amino}methyl]ferrocenes and their cyclometallated complexesCondensation of aminomethylferrocene and substituted benzaldehydes resulted in aldimines and followed by reduction with sodium borohydride to give secondary amines. N-methylation of secondary amines with HCHO/NaCNBH3/HOAc led to tertiary ferrocenylamines. Treatment of tertiary ferrocenylamines with Hg(OAc)2 or Na2PdCl4 or PtCl2(DMSO)2 afforded the corresponding cyclomatallated complexes(M = Hg, Pd, Pt).2. Synthesis, characterization of [{(N-methyl-N-p-R-benzyl)amino}benzyl]ferrocenes and their cyclopalladated complexesCondensation of benzoylferrocene and substituted benzylamines produced ferrocenylketimines which were followed by reduction with sodium borohydride to give secondary amines. By contrast to our previous method for N-methylation of sec-amines, the tert-Ferrocenylamines derived from benzoylferrocene were synthesized by N-methylation of the corresponding sec-amines with CH3I as the methylation reagent and t-BuOK as the base. Treatment of tertiary ferrocenylamines with with Na2PdCl4 in the presence of NaOAc afforded the corresponding cyclopalladates.3. Synthesis, characterization of chiral tert-ferrocenylamines and their cyclopalladatesCondensation of (R) and (S)-α-methylbenzylamines and ferrocenecarboxaldehyde resulted in aldimines. Reduction of these imines afforded the chiral sec-ferrocenylamines, N-methylation of these sec-amines gave chiral tert- ferrocenylamines with the configurations of R, S respectively. Treatment of amines with Na2PdCl4 afforded corresponding cyclopalladates bearing chriality with three elements, i.e., (R_NR_CR_P) and (S_NS_CS_P). 4. Studies on the possible mechanism for the cyclomatallationsThe possible mechanism for the formation of cyclomatallations (M = Hg, Pd, Pt) was discussed. For the ortho-mercuration, it is assumed that an intramolecular N-Hg coordination pattern in these ortho-mercurated ferrocenylamines is present compared to our earlier results. For cyclopalldation or platination, since the N-reversion in these tert-ferrocenylamines, the coordination of metal with N atom from two sides led to the coordinated intermediates and then the preferrable activation of its adjacent C-H bonds in cyclopentadienyl ring was observed.5. Studies on the catalysis of the cyclopalladates in carbon-carbon bond cross coupling reactionsUnder the optimized condition, the cyclopallates could catalyze the Suzuki coupling of aryl chlorides with phenylboronic acid where aryl group ranged from electron-donating to electron-withdrawing group. In addition, the Heck reaction of bromobenzene with styrene of a wide range of substrates was also achieved. Both Suzuki and Heck coupling reactions proceeded with high efficiency. Using appropriate surfactants, these cyclopalladates can also catalyze Heck coupling reaction in water.6. Studies on the antitumor activity of cycloplatinated complexesConfirmed by qualitative and quantitative tests, the cycloplatinated complexes have good activity to inhibit A549 cell and Hela cell.