Synthesis Of Novel C2-symmetric Chiral Tetraaza Ligands And Their Ru(Ⅱ)、Rb(Ⅲ)、Ir(Ⅲ) Complexes Catalyzed Asymmtric Transfer Hydrogenation Of Ketones

Optically active aromatic secondary alcohols are very useful chemical products and are very extensive application in pharmaceuticals,agrochemicals,fragrances and fine chemicals,Chiral aromatic secondary alcohols,such as α-phenylethanol,the most basie and common chiral compounds, are of great significance.Asymmetric transfer hydrogenation of aromatic ketones is now realized to be one of the most powerful,practical and versatile tools to access chiral alcohols.In particular,the organo-metellic complexes with chiral N-tosylated diamines for the asymmetric transfer hydrogenatiion of aromatic ketones demonstrate remarkably high catalytic activities.However, C2-symmetric chiral tetramine ligand and metal complexes of aromatic ketones catalyzed by asymmetric transfer hydrogenation is challenging research topic,So synthesis of stable,efficient chiral amine ligand,to find catalytic conditions are very important significance.Firstly,This artical is based on (1S,2S)-(+)-1,2-diphenylethylenediamine and1,3Benzenedisulfonyl chloride synthetic materials,throughthe dual-sulfonylreaction synthesis of new C2-symmetric chiral amine ligand and metal complexes [RuCl2(p-cymene)]2,[Cp*RhCl2]2,[Cp*IrCl2]2, RuCl2, RhCl3etc.with Ligard and isopropanol/KOH as the reaction system,and isoproanol as the hydrogen source of the catalytic reactioin for the asymmetric transfer hydrogenation of acetophenone,3nitrophenyl ethyl ketone, etc.reactionThe experimental results show that:(1)The C2-symmetric chiral amine ligand with RuCl2(p-cymene.)]2"in situ" of Acctophenone Catalyzed by the conversion rate of70%-86%, ee value as high as99.9%,C2-symmetric chiral terraamine ligand with [Cp*RhCl2]2"in situ" acetophenone Catalyzed conversion rate of80%-90%,the ee.value obtained is only5%-17%, C2-symmetric chiral amine ligand and metal complexes [Cp*IrCl2]2"in situ" acetophenone Catalyzed conversion rate of72%-82%,the obtained ee value of52%.[Cp*RhCl2]2,[Cp*IrCl2]2two kinds of catalytie results obtained by complex catalysts compared with RuCl2(p-cymene,)]2: ee value deerease too obvious(2) C2-symmetric chiral amine ligands with RuCl2(p-cymene,)]2with the formation of catalysts3-the nitroacetophenone catalytic conversion rate of69%-79%,and only35%-47%ee vaute. Acetophenone Catalyzed by the results obtained, We can get conclusion that: Bring up this worse result may be due to the3nitroacetophenone-NO2with electron withdrawing ability of redueing the catalytic offect in catalysis.(3) C2-symmetric chiral amine ligands with [Cp*RhCl2]2"in situ"the catalytic3-Nitroacetophenone,get the conversion rate of71%-80%. ee vaule of68%-76%of C2-symmetric chiral amine ligands with [Cp*IrCl2]2"in situ" catalyst nitroacetophenone get the conversion rate of69%-79%ee vaule to60%-74%(4) C2symmetric chiral amine ligands with RuCl2compounds with the formation of the catalyst on the conversion of3-nitroacetophenone rate of6%-79%ee vaule of2%-16%, C2symmetrychiral amine ligand with the RhCl3compound to form a catalyst "in situ" of Acetophenone Catalyzed get the conversiion rate of68%-80%,the ee vaule of7%-22%.The effects of reaction temperature,catalyst system aids potassium hydroxide the reaction time of acctophenone,3-the nitroacetophenone asymmetric hydrogen transfer reactions, the optimum reactiion conditions of60℃,and thinlayer chromatography to track the reaction process,acetophenone/potassium hydroxide/catalyst=100:40:1optimum reaction conditions were60℃,3-nitroacetophenone/potassium hydroxide/catayst=100:80:1.The results demonstrate that the catalytic asymmetric reaction with the operating conditions are mild,a litter by-product,and good conversion rate,etc.,so research synthesis of novel chiral amine ligand is of positive significance.