手性联萘基-2,2'-联吡啶及其衍生物的合成及其在不对称合成中的应用  

Synthesis of Chiral Binaphthyl 2,2'-Bipydine and Its Derivatives and Their Application to Asymmetric Synthesis

作　　者：李玉邯[1] 金日哲[2] 高连勋[2] 

机构地区：[1]吉林工商学院食品工程学院,长春130507 [2]中国科学院长春应用化学研究所,长春130022

出　　处：《应用化学》2016年第7期792-797,共6页Chinese Journal of Applied Chemistry

摘　　要：利用Krhnke方法,以芳基乙酮为原料一锅法简洁地合成了6-芳基-6'-溴-2,2'-联吡啶2b^2d。通过(R)-3-(4,4,5,5-四甲基-1,3,2-二噁唑硼烷基)-2,2'-乙氧基-1,1'-联萘((R)-1)与6-溴-2,2'-联吡啶及其衍生物2a^2d的Suzuki偶联,合成了4种手性6-[3-((R)-2,2'-二乙氧基-1,1'-联萘)基]-2,2'-联吡啶(R)-3a^3d。将配体(R)-3a^3d应用于苯乙酮的不对称氢转移反应中,配体(R)-3a给出92%的转化率和4%的对映体过量(ee)值。6-Aryl-6＇-bromo-2,2＇-bipyridine derivatives 2b ~ 2d were synthesized efficiently from aryl-ethanone by the Krhnke method in one-pot. Then,four chiral 6-[3-（（ R）-2,2＇-diethoxyl-1,1＇-binaphthyl） ]-2,2＇-bipyridine ligands（ R）-3a ~ 3d were synthesized by Suzuki coupling of（ R）-3-（ 4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl）-2,2＇-diethoxyl-1,1＇-binaphthyl（ R）-1 with 6-bromo-2,2＇-bipyridine derivatives 2a ~ 2d.These ligands were applied to asymmetric transfer hydrogenation of acetophenone. The ligand（ R）-3a affords92% of conversion and 4% enantiomeric excess（ ee）.

关 键 词：联吡啶 手性 联萘酚 

分 类 号：O626.3[理学—有机化学]