新手性配体的合成及其催化不对称氨羟化反应研究.pdfVIP

2005 25 Vol. 25, 2005 8 , 982986 Chinese Journal of Organic Chemistry No. 8, 982986 · · (QN) AQN 2 堃 * ( 710032) AlCl3 , , Friedel-Crafts , 60%1,4-. 1,4-(QN)2AQN, 85%. N-, (QN) AQN OsO 2 4 (90%96% ee)(75 2598 2), 50% 70%, . , , , α- . ; (QN)2AQN; β-; α- Synthesis of a New Chiral Ligand (QN) AQN and Its Application to 2 the Catalytic Asymmetric Aminohydroxylation of Methyl Cinnamates CHENG, Si-Kun ZHANG, Sheng-Yong* SUN, Xiao-Li JIANG, Ru WANG, Qiao-Feng (Department of Chemistry, School of Pharmacy, The Fourth Military Medical University, Xian 710032 ) Abstract 1,4-Difluoroanthraquinone was obtained in 60% yield by Friedel-Crafts reaction of phthalic an- hydride and 1,4-difluorobenzene in the presence of AlCl3 followed by cyclization with polyphosphoric acid. Then the ligand (QN)2AQN was prepared by nucleophilic substitution of 1,4-difluoroanthraquinone with the lithium salt of quinine in 85% yield. In the presence of benzyl N-chlorocarbamate (the oxidant and nitrogen source), five methyl cinnamates gave the vicinal amino alcohols via asymmetric aminohydroxylation (AA) catalyzed by (QN) AQN-OsO complex in excellent enantioselectivities of 90%96% ee, normal to high 2 4 regioselectivities of 75 2598 2 and good yields of 50%70%. These results were compar