两种不对称二羟化反应的新型手性配体的合成及其应用  

Synthesis and utilization of two novel chirl liands for asymmetric dihydroxylation

作　　者：王巧峰[1] 孙晓莉[1] 金瑛[1] 尉琳琳[1] 何炜[1] 

机构地区：[1]第四军医大学基础部化学教研室,陕西西安710033

出　　处：《第四军医大学学报》2004年第11期973-975,共3页Journal of the Fourth Military Medical University

基　　金：国家自然科学基金 (2 0 2 72 0 82 )

摘　　要：目的 :设计两种新的桥联基以合成两种新的不对称二羟化反应的金鸡纳碱衍生物配体并将其用于催化四种烯烃的不对称二羟化反应 ,考察催化效果 .方法 :以苯酚、α 萘酚和氰尿酰氯为原料 ,制备两种新桥联基 ,然后在氮气保护下 ,于5 0℃分别与奎宁反应生成两个新配体 ,并将其用于锇酸钾 铁氰化钾、H2 O tBuOH(1∶1 )体系 ,催化四种烯烃的不对称二羟化反应 .结果 :结果表明 ,化学产率为 75 %～ 98% ,对映体过量均大于 80 % .结论 :以氰尿酰氯衍生物为桥联基合成的两种奎宁金鸡纳碱衍生物配体 ,方法简便、成本低廉 。AIM: To synthesize two novel cinchona alkaloid derived ligands for asymmetric dihydroxylation (AD) of olfins and catalyze AD reactions of four olfins. METHODS: Two kinds of new bridge agents prepared from phenol, α naphthol and cyanuryl chloride reacted with quinine in N,N dimethylformamide (DMF) and NaH at 50℃ under N 2 to yield the chiral ligands A and B. The AD reactions of olfins were performed in H 2O t BuOH (1∶1) using the ligand A or B K 2OsO 2 (OH) 4 as catalyst. RESULTS: The applications of the two ligands A and B to AD of four olfins produced four corresponding chiral diols, respectively in 75%-85% yields and >80% ees. CONCLUSION: Higher yields and better enantiomeric excess can be obtained by catalytic asymmetric dihydroxylation of the four olfins with the two new ligandsA and B.

关 键 词：氰尿酰氯 金鸡纳碱衍生物 不对称二羟化 

分 类 号：O625.6[理学—有机化学]