Nitrogen-containing Chiral Ligands, Metal Complexes Of The Racemic Ligand Catalyst Acetophenone Asymmetric Transfer Hydrogenation Reaction

This thesis mainly contains the importance of synthesizing optically active phenyl secondary alcohols and all kinds of preparation methods of the optically active phenyl secondary alcohols.Since the optically active phenyl secondary alcohol is important mediums of many effective medicines,it is necessary to be studied in the area of pharmaceutical chemistry. The methods of synthesizing the optically active phenyl secondary alcohols can be divided into three kinds: I .Reacti- ons with chiral reagents~ 2.Enantioselective addition reduction of carbonyl.3.Asym- metric catalytic hydrogenation. The hydride transfer reduction belongs to asymme- tric catalytic hydrogenation. Because the operation is easy ,not using metal hydride or hydrogen, the hydride transfer reduction becomes a effective method for preparing the secondary alcohols. The catalyst consisting of optically active ligand and transition metal complex and the catalyst consisting of racemic ligand ~. transition metal complex and chiral activator can both realize the enantioselective hydrogenation. In this thesis, a chiral activator (IS,2S) ?and (1R,2R)-1,2-diphenyl ethylenediamine,optically active ligand (1 S,2S) ?and (1R,2R)- N-p-toluenesulfonyl- 1 ,2-diphenylethylenediamine, racemic ligand 2,2~-diamino-1, 1?binaphthyl and transition metal complex bis(cycloocta-1,5-diene)- ii Lt -dichlorodirhodium were prepared. The reactional processes conditions and operations were all studied The products were characterized by melting points infrared spectra~ element analysis and 慔NMR spectra. The results of all the experiments show that: I~. The syntbesization and purification of the isomarine are the keys to the synthesis of 1,2-diphenyl ethylenediamine. The reaction tempreture .. time and the purification of every step product are all influential to the final product. During the optical resolution of 1,2-diphenyl ethylenediamine, fully stirring is very important. 2~ the optimum in which the N-p-toluenesulfonyl-l 2-diphenyl ethylenediamine got the higher yield is: the reaction tempreture ca.00C, the reaction time 24h, acidification level PH=3.3 The higher yield of 2,2-diamino- 1,1 -binaphthyl was got under the optimum reaction condition: the reaction vessel autoclave, the reaction tempreture ca. I 800C, the reaction time 48h.The mixture was recrystallized with hot methol-hydrochloric acid (v/v=4:1)and diethyl ether. The catalyst consisting of optically active ligand (IS,2S) 桸-p-toluenesulfonyl -1,2-diphenyl ethylenediamine and transition metal complex bis(cycloocta-1,5-diene)- II -dichlorodirhodium and the catalyst consisting of racemic ligand 2,2-diamino- 1,1-binaphthyl,transition metal complex bis(cycloocta-1,5-diene)- L?li -dichlorodi rhodium and the chiral activator (1S,2S) ?1,2-diphenyl ethylenedianiine were used to catalyze the hydride transfer reduction of acetophenone in 2-propanol. The 3 product was characterized and analysized by gas chromatograph and polarimeter. The results show that: the two different catalytic systems both have the activities of enantioselective hydrogenation.The configuration of the catalyst decides the configuration of excess optical isomer in the product. The configuration of the products got in the reactions catalysed by the catalyst consisting of (1 S,2S)-N-p-toluenesulfonyl- 1 ,2-diphenyl ethylenediamine and the catalyst consisting of(1S,2S)-1,2-diphenyl ethylenediamine is R.The catalytic cycle mechanisms were also discussed . By discussing we know that the...