奎宁和辛可宁衍生物的合成及其在不对称双羟化反应中的催化作用  

Synthesis of quinine and cinchonine derivatives and their catalytic performance in asymmetric dihydroxylation

作　　者：何炜[1] 刘鹏[1] 金瑛[1] 辛春艳[1] 张生勇[1] 

机构地区：[1]第四军医大学药学系化学教研室,陕西西安710033

出　　处：《第四军医大学学报》2006年第12期1150-1152,共3页Journal of the Fourth Military Medical University

基　　金：国家自然科学基金面上项目(20372083);陕西省自然科学基金项目(2002B20)

摘　　要：目的：合成两种新的金鸡纳生物碱类衍生物配体并将其用于催化五种烯烃的不对称二羟化反应，考察催化效果．方法：以价廉易得的奎宁和辛可宁为原料，经过结构转换得到9-氨基奎宁和9-氨基辛克宁，进而与对氯苯甲酰氯反应制得两种新型手性配体，并将其用于锇催化的烯烃的不对称双羟化反应．结果：在五种烯烃的不对称双羟化反应中，化学产率为87％～95％，对映体过量值为76％～93％．结论：两种对氯苯甲酰胺类新型手性配体合成方法简便、成本低廉、性质稳定，对烯烃的不对称二羟化反应有较强的催化活性和光学选择性．AIM： To synthesize 2 novel chiral ligands derived from cinchona alkaloids and study their catalytic performance in asymmetric dihydroxylation （AD） of 5 olefins. METHODS： Inexpensive quinine and cinchonine were transformed to 9-NH2- quinine and 9-NH2-cinchonine, which reacted with 4-chlorobenzoyl chloride to afford 2 novel chiral ligands. The AD reactions of olefins were performed in H2O-^1BuOH （1：1） using the 2 ligands-K2OsO2 （ OH ）4 as catalysts. RESULTS： The applications of the 2 ligands in AD of 5 olefins produced 5 corresponding chiral diols, respectively in 87% -95% yields and 76% -93% enantiomeric excess. CONCLUSION： 2 novel stable chiral ligands were synthesized by simple and inexpensive methods. When they were used in catalytic AD, high yields and enantiomeric excess of the products were observed.

关 键 词：奎宁 辛可宁 不对称双羟化反应 

分 类 号：O625.6[理学—有机化学]