【摘要】：手性聯(lián)萘酚是一種多功能試劑,聯(lián)萘酚及其衍生物在不對(duì)稱催化、不對(duì)稱誘導(dǎo)螺旋聚合以及手性識(shí)別等方面被廣泛應(yīng)用并受到越來越多的關(guān)注。本文的主要內(nèi)容分為三大部分:(1)聯(lián)萘酚聚合物的合成及其表征。以(S)-聯(lián)萘酚為原料,參照現(xiàn)有的文獻(xiàn)資料合成了(S)-6-甲�；�-2,2′-雙(甲氧基甲氧基)-1-1′-聯(lián)萘。該中間化合物進(jìn)一步經(jīng)格氏試劑加成和Dess-Martin Periodinane(DMP)氧化得到手性單體(6-丙烯�；�-2,2′-雙甲氧甲氧基-1,1′-聯(lián)萘,縮寫成Acr M)及其單元類似物(6-丙�；�-2,2′-雙甲氧甲氧基-1,1′-聯(lián)萘,縮寫成U-AcrM)。從(S)-聯(lián)萘酚出發(fā),經(jīng)過氯甲基甲醚保護(hù)羥基,正丁基鋰拔氫,3-位二苯羥甲基化和3′-位甲�；玫铰�(lián)萘酚的醛衍生物,再經(jīng)Wittig反應(yīng)得到單體(3-二苯羥甲基-3′-乙烯基-2,2′-雙甲氧甲氧基-1,1′-聯(lián)萘,縮寫成DPVB0),脫除甲氧甲基保護(hù)基后得手性聯(lián)萘單體(3-二苯羥甲基-3′-乙烯基-2,2′-二羥基-1,1′-聯(lián)萘,縮寫成DPVB1)。DPVB1的單體單元(3-二苯羥甲基-3′-乙基-2,2′-二羥基-1,1′-聯(lián)萘,縮寫成U-DPVB1)由DPVB1經(jīng)過Pd/C-HCOONH4還原制得。兩種聯(lián)萘酚手性單體Acr M和DPVB1通過自由基聚合分別得到聚合物P-Acr M和P-DPVB1。所有化合物結(jié)構(gòu)經(jīng)1HNMR,13CNMR,旋光等表征。P-AcrM和P-DPVB1系列化合物的圓二色譜測試結(jié)果表明,這兩種聚合物在溶液中都具有單一螺旋過量。(2)聯(lián)萘酚聚合物衍生物催化不對(duì)稱催化HDA反應(yīng)初探。研究了P-DPVB1-硼的新型Lewis酸催化劑催化的苯甲醛與Danishefsky雙烯的不對(duì)稱雜Diels Alder反應(yīng),對(duì)反應(yīng)經(jīng)溶劑、Lewis酸和溫度等條件篩選獲得了較好的對(duì)映選擇性。聚合物配體P-DPVB1的HDA催化不對(duì)稱誘導(dǎo)效果優(yōu)于單體DPVB1和單體單元U-DPVB1,且可以回收重復(fù)使用并保持原有的催化活性,體現(xiàn)了螺旋聚合物在不對(duì)稱催化中的優(yōu)越性。(3)從DPVB0出發(fā)合成了三種含乙烯基和二苯甲基的(S)-BINOL衍生物并用于手性α-甲基芐胺的手性熒光識(shí)別。三種熒光化合物:3-二苯羥甲基-3′-乙烯基-2,2′-二羥基-1,1′-聯(lián)萘(縮寫成DPVB1),3-二苯甲基-3′-乙烯基-2,2′-二羥基-1,1′-聯(lián)萘(縮寫成DPVB2)和3-二苯甲氧基甲基-3′-乙烯基-2,2′-二羥基-1,1′-聯(lián)萘(縮寫成DPVB3)的熒光光譜與在0.2-1.0×10-5 M(CH2Cl2)濃度范圍內(nèi)呈良好的線性關(guān)系(R2:0.993-0.998)。1H NMR實(shí)驗(yàn)和熒光猝滅實(shí)驗(yàn)表明這三種熒光化合物對(duì)手性α-甲基芐胺具有對(duì)映選擇性識(shí)別能力,對(duì)映選擇性因子分別為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，

本文編號(hào)：2494509