Ⅰ. Selective Synthesis Of Unsymmetrical Ethers Catalyzed By NaHSO₃ Ⅱ. Research On The Synthesis And Property Of Organometallic Complexes With D-Camphoric Derivate Ligands

This dissertation can be divided into two parts:（i） Selective synthesis of unsymmetrical benzylic ethers catalyzed by sodium bisulfite and studies on the mechanism, （ii） Synthesis and catalytic property investigations of ruthenium and iridium organometallic complexes using D-camphoric diamine or its derivatives as ligands.In the first project, we demonstrated an efficient method for the synthesis of unsymmetrical ethers from benzylic alcohols bearing electron-donating groups with primary or secondary aliphatic alcohols catalyzed by 1 mol% NaHS03 in the absence of solvents with high yields and satisfying selectivity. Besides, we also investigated the feasibility of intramolecular etherfication of diols.To disclose the mechanisim of the reaction, we carried out two experiments. On the one hand, catalyzed by NaHSO₃,（S）-1-（4-methoxyphenyl）ethanol gave racemization product; on the other hand, we obtained optical product with （S）-2-butanol. This suggests that the reaction involves a benzylic carbocation intermediate.In the second project, using D-camphor as the very starting material, we obtained D-camphoric diamine and Ru/Ir cationic metallic complexes were successfully synthesized with the diamine. Then we prepared a series of Ru/Ir organometallic complexes with D-camphoric derivative ligands and the structures of four compounds are confirmed by X-ray crystallography analysis.In the following work, we made great efforts to test the catalytic properties of RuCl[κ²（N,N¹）-（1S,3S）-N-（3-amino-2,2,3-trimethylcyclopentyl）-4-methylbenzenesulf onamide]（η⁶-p-cymene） in assymetric synthesis such as asymmetric transfer hydrogenation, asymmetric catalytic hydrogenation and nitrile hydration. It’s proved that this organometallic compound showed moderate catalytic activity in asymmetric transfer hydrogenation in the solvent of HCOOH/TEA/H₂O while the stereoselectivity should be improved in further research.