手性氨基醇诱导联苯构象转化制备轴手性联苯化合物  

Preparation of Axially Chiral Biphenyls by Configuration Transformation Based on Chiral Amino Alcohols

作　　者：王利敏[1] 程森祥[1] 陈彤[1] 常俊标[1,2] 

机构地区：[1]河南省科学院高新技术研究中心,郑州450002 [2]郑州大学化学系,郑州450001

出　　处：《化学学报》2012年第10期1201-1206,共6页Acta Chimica Sinica

基　　金：国家杰出青年科学基金(No.30825043);国家自然科学基金(No.20572017)资助项目~~

摘　　要：在(S)-氨基丙醇及(R)-氨基丙醇手性臂的作用下,(M/P)-4,4'-二甲氧基-5,6,5',6'-二次甲二氧基-2-甲酸酯-2'-甲酰氨联苯经构型转化,制备了光学纯轴手性联苯化合物(P,S)-3a和(M,R)-3b.测定了(P,S)-3a的晶体结构及CD光谱.结果表明,化合物(P,S)-3a晶体属单斜晶系,P2(1)空间群,晶胞参数为a=12.122(2),b=8.9911(18),c=12.779(3),β=112.38(3)°,在晶体中存在两组分子间氢键相互作用,一组氢键由羟基氢与另一分子酰胺基团的羰基氧组成O—H…O,另一组由酰胺基团的NH与另一分子酰胺基团的羰基氧构成N—H…O,每一分子通过四个氢键与另外两个分子相连,构成棒状结构.由CD光谱确定了(M,R)-3b的立体构型.此外,由(P,S)-3a合成了轴手性化合物(P)-2,2'-二羟甲基-4,4'-二甲氧基-5,6,5',6'-二亚甲二氧基-联苯(6a).Axially chiral biphenyls（P,S）-3a and（M,R）-3b were obtained from（M/P）-4,4＇-dimethoxy5,6,5＇,6＇-bis（methylenedioxy）-2-carboxylester-2＇-carboxamide biphenyls via configuration transformation of the biphenyls with（S）-alaninol or（R）-alaninol chiral-arm.Crystal structure of（P,S）-3a was determined.The crystal of（P,S）-3a belongs to monoclinic,space group P2（1）,a=12.122（2）,b=8.9911（18）,c= 12.779（3）,β=112.38（3）°.There are two kinds of hydrogen-bonding in the（P,S）-3a crystal.The first is hydrogen-bonding between the hydroxyl group of the amino alcohol arm and the amide oxygen of a neighboring molecule.The second is hydrogen-bonding between the amide hydrogen atom and the amide oxygen of a neighboring molecule.Each molecule is linked to its two adjacent molecules by four intermolecular H-bonds.The configuration of（M,R）-3b was assigned based on the CD spectra.In addition,from（P,S）-3a,（P）-2,2＇-dihydroxymethyl-4,4＇-dimethoxy-5,6,5＇,6＇-bis（methylenedioxy）-biphenyl（6a） was synthesized.

关 键 词：轴手性联苯 诱导结晶 构型转化 

分 类 号：O621.2[理学—有机化学]