螺旋聚[(S)-3-(二苯羟甲基)-3′-乙烯基-2,2'-二羟基-1,1'-联萘]的合成、光学性质及其在杂-Diels-Alder反应中的不对称诱导  

Synthesis and Optical Properties of Helical Poly[(S)-3-hydroxyldiphenylmethyl-3'-vinyl-2,2'-dihydroxy-1,1'-binaphthyl] and Its Use in Asymmetric Hetero-Diels-Alder Reaction

作　　者：晏瑾懿 阳珠生 阳年发[1] 

机构地区：[1]湘潭大学化学学院环境友好化学与应用省部共建教育部重点实验室,湘潭411105

出　　处：《有机化学》2016年第4期812-817,共6页Chinese Journal of Organic Chemistry

基　　金：国家自然科学基金(No.21172186);高等学校博士学科点专项科研基金(No.20134301110004)资助项目~~

摘　　要：合成了一种基于联萘酚的新型手性单体,(S)-3-(二苯羟甲基)-3'-3-乙烯基-2,2'-二羟基-1,1'-联萘(5).通过由偶氮异丁腈(AIBN)引发的自由基聚合得到聚[(S)-3-(二苯羟甲基)-3'-3-乙烯基-2,2'-二羟基-1,1'-联萘](P-5),旋光、紫外-可见光谱、圆二色谱表征结果表明P-5以单手性螺旋结构的形式存在于溶液中.考察了螺旋齐聚物P-5在催化苯甲醛与Danishefsky双烯烃的杂-Diels-Alder(HDA)反应中的不对称诱导作用,所得加和产物的ee值达71%,P-5可以被回收重复使用而保持催化活性不变.A novel binaphthol-based monomer, 3-hydroxydiphenylmethyl-3＇-vinyl-2,2＇-dihydroxy-1,1＇-binaphthyl was synthesized and polymerized using azodiisobutyrodinitrile（AIBN） as an initiator to afford the polymer P-5. Polarimetry, UV-Vis and circular dichroism spectroscopy characterizations indicated that the polymer existed in the form of one-handed helical structure in solution. The application of helical polymer P-5 in catalytic asymmetric hetero-Diels-Alder（HDA） reaction between benzaldehyde and Danishefsky＇s diene has been studied, resulting in the target product with 71% ee. P-5 can be easily recovered and reused without loss of catalytic activity.

关 键 词：合成螺旋聚合物 联萘 杂Diels-Alder反应 不对称催化 

分 类 号：O621.251[理学—有机化学] O631.5[理学—化学]