手性氨基醇诱导联苯构象转化制备轴手性联苯化合物

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)-3a. 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) Å, b＝8.9911(18) Å, c＝12.779(3) Å, 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).

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

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.