联萘酚衍生物聚合物的合成及其在催化不对称Hetero-Diels-Alder反应和手性荧光识别中的应用

发布时间：2019-06-06 18:24

【摘要】：手性联萘酚是一种多功能试剂,联萘酚及其衍生物在不对称催化、不对称诱导螺旋聚合以及手性识别等方面被广泛应用并受到越来越多的关注。本文的主要内容分为三大部分:(1)联萘酚聚合物的合成及其表征。以(S)-联萘酚为原料,参照现有的文献资料合成了(S)-6-甲酰基-2,2′-双(甲氧基甲氧基)-1-1′-联萘。该中间化合物进一步经格氏试剂加成和Dess-Martin Periodinane(DMP)氧化得到手性单体(6-丙烯酰基-2,2′-双甲氧甲氧基-1,1′-联萘,缩写成Acr M)及其单元类似物(6-丙酰基-2,2′-双甲氧甲氧基-1,1′-联萘,缩写成U-AcrM)。从(S)-联萘酚出发,经过氯甲基甲醚保护羟基,正丁基锂拔氢,3-位二苯羟甲基化和3′-位甲酰化得到联萘酚的醛衍生物,再经Wittig反应得到单体(3-二苯羟甲基-3′-乙烯基-2,2′-双甲氧甲氧基-1,1′-联萘,缩写成DPVB0),脱除甲氧甲基保护基后得手性联萘单体(3-二苯羟甲基-3′-乙烯基-2,2′-二羟基-1,1′-联萘,缩写成DPVB1)。DPVB1的单体单元(3-二苯羟甲基-3′-乙基-2,2′-二羟基-1,1′-联萘,缩写成U-DPVB1)由DPVB1经过Pd/C-HCOONH4还原制得。两种联萘酚手性单体Acr M和DPVB1通过自由基聚合分别得到聚合物P-Acr M和P-DPVB1。所有化合物结构经1HNMR,13CNMR,旋光等表征。P-AcrM和P-DPVB1系列化合物的圆二色谱测试结果表明,这两种聚合物在溶液中都具有单一螺旋过量。(2)联萘酚聚合物衍生物催化不对称催化HDA反应初探。研究了P-DPVB1-硼的新型Lewis酸催化剂催化的苯甲醛与Danishefsky双烯的不对称杂Diels Alder反应,对反应经溶剂、Lewis酸和温度等条件筛选获得了较好的对映选择性。聚合物配体P-DPVB1的HDA催化不对称诱导效果优于单体DPVB1和单体单元U-DPVB1,且可以回收重复使用并保持原有的催化活性,体现了螺旋聚合物在不对称催化中的优越性。(3)从DPVB0出发合成了三种含乙烯基和二苯甲基的(S)-BINOL衍生物并用于手性α-甲基苄胺的手性荧光识别。三种荧光化合物:3-二苯羟甲基-3′-乙烯基-2,2′-二羟基-1,1′-联萘(缩写成DPVB1),3-二苯甲基-3′-乙烯基-2,2′-二羟基-1,1′-联萘(缩写成DPVB2)和3-二苯甲氧基甲基-3′-乙烯基-2,2′-二羟基-1,1′-联萘(缩写成DPVB3)的荧光光谱与在0.2-1.0×10-5 M(CH2Cl2)浓度范围内呈良好的线性关系(R2:0.993-0.998)。1H NMR实验和荧光猝灭实验表明这三种荧光化合物对手性α-甲基苄胺具有对映选择性识别能力,对映选择性因子分别为1.04,1.43,2.04。
[Abstract]:Chiral binaphthol is a multifunctional reagent. Binaphthol and its derivatives have been widely used in asymmetric catalysis, asymmetric induced spiral polymerization and chiral recognition. The main contents of this paper are divided into three parts: (1) Synthesis and characterization of binaphthol polymers. Using (S)-binaphthol as raw material and referring to the existing literature, (S)-6-formyl-2, 2 (methoxyl)-1 and binaphthalene were synthesized. The intermediate compound was further prepared by Grignard reagent addition and Dess-Martin Periodinane (DMP) oxidation to give chiral monomers (6-acrylic-2, 2)-dimethoxyl-1, 1 / binaphthalene, Abbreviated to AcrM) and its unit analogues (6-propionyl-2, 2 o-dimethoxy-1, 1 o-binaphthalene, abbreviated to U-AcrM). Starting from (S)-binaphthol, the aldehyde derivatives of binaphthol were obtained by chloromethyl methyl ether protected hydroxyl group, n-Ding Ji lithium hydrogen extraction, 3-diphenyl hydroxymethylation and 3 / 3 formylation. The monomer (3-diphenylhydroxymethyl-3 o-vinyl-2, 2 o-dimethoxy-1, 1 o-binaphthalene, abbreviated as DPVB0) was obtained by Wittig reaction. Chiral binaphthalene monomers (3-diphenylhydroxymethyl-3 / vinyl-2, 2 / dihydroxyl-1, 1 / binaphthalene) were obtained by removing methoxymethyl protection group. The monomer unit (3-diphenylhydroxymethyl-3-ethyl-2, 2-dihydroxymethyl-1, 1 o-binaphthalene, abbreviated as U-DPVB1) was prepared by Pd/C-HCOONH4 reduction of DPVB1. Two kinds of binaphthol chiral monomers Acr M and DPVB1 were obtained by free radical polymerization. The polymers P-Acr M and P 鈮，

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