金银花抗病毒有效成分双抗素类似物的合成与活性研究
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摘要
双抗素(Shuangkangsu,1t),是本课题组从治疗感冒的常用中药金银花中分离发现的一种具有新型骨架结构的环状过氧化物糖苷,因其分子中含有少见的六元过氧环系而成为首次发现的天然含过氧环结构抗病毒有效成分,对鸡胚内流感病毒和呼吸道合胞病毒有明显抑制作用,是值得重视的创新药物先导物。
本课题从双抗素及其类似物的全合成研究入手,在本课题组已有的工作基础上发展了双抗素类分子中过氧键环系的合成方法,进一步研究了该类环状过氧半缩醛羟基的稳定性及有关反应活性,探索了该类化合物糖苷化以及糖基脱保护的方法,深入研究了三烯的合成,合成了双抗素结构类似物和简化物并对其进行了体外活性评价(包括抗病毒作用和抗肿瘤作用两方面),对实验中发现的新方法的适用性及有关反应特性进行了较为系统的研究。
主要完成了如下研究工作:
一、发展了双抗素类分子中过氧键环系的形成方法,即直接采用过氧化氢的水溶液在较低温度下对邻苯二甲醛进行分子内加成形成环过氧二半缩醛,简化了后处理,提高了产率,为后续反应提供更为充足的原料。用同样方法合成了含氧七员环状共轭三烯并环过氧二半缩醛化合物92和101,首次对其前体含氧七员环状共轭三烯邻二甲醛91和100的合成做了较为系统的研究并对其反应过程做了初步的探讨。
二、以化合物1为底物,结合本课题组已有的相关工作积累,进一步研究了双抗素类分子中环过氧化二半缩醛羟基的稳定性及有关反应活性,探索了该类化合物的糖苷化和脱乙酰保护基的方法,以硫苷为糖供体、NIS/AgOTf为催化剂的方法,三氯亚胺酯糖苷为糖供体、三氟化硼乙醚或者三甲基硅基三氟甲磺酸银为催化剂在低温无水无氧条件下对化合物1进行糖苷化反应,是比较适宜的方法。对过氧二半缩醛糖苷的脱乙酰保护基的方法也做了探索,发现二丁基氧化锡是37,38,93,94,102和103脱乙酰保护基的较为适宜的方法。按上述方法,分别以化合物1、92和101为底物,合成了光活纯的双抗素类似物39,40,95,96,104和105,其绝对构型通过与绝对构型已知的化合物6,7及双抗素分子进行有关CD谱比较的方法加以确定。对本课题有关的一些反应的机理作了初步探讨。
三、合成了双抗素类分子的系列简化物,对所合成的双抗素类似物和简化物进行了抗流感病毒和抗肿瘤活性筛选,并对其构效关系和作用机理进行了初步探讨。
四、进一步研究了在酸、碱或加热条件下,该类过氧化物中过氧键断裂的机理。
五、深入研究了共轭三烯片段的合成,发现了一步合成某些含氧或含氮杂原子的七员环共轭三烯邻二甲酸酯类化合物的新方法,首次较为系统地研究了其适用性和相关的反应特性。
Shuangkangsu, a new component with an unusual 1,2-dioxine skeleton first isolated by our group from a TCM (traditional Chinese medicine) named Jinyinhua, has a significant activity of inhibition of influenza virus in chicken embryo and respiratory syncytial virus in cells. The particular skeleton of the leading compound is valuable for new drug research and development.
For studying the total synthesis of Shuangkangsu and its analogs, in this work, the methods for the formation and glucosylation of 1,4-Dihydro-[1,2]dioxine-1,4-diol as well as the method for removal of acetyl protective group in compounds 37, 38 have been studied. Synthesis of 1,3,5-triene had been further studied and analogs of Shuangkangsu were synthesized before tested for bioactivities including antiviral activitives and antitumor activities in vitro. Meanwhile, some new synthetic methods have been found and some of the related reactions in this work have also been studied.
1. The ameliorative method for the formation of 1,4-Dihydro-[1,2]dioxine-1,4-diol, which is an intramolecular addition of hydrogen peroxide to 1,2-dialdehyde was established. This ameliorative method was used to simplify the procedure and improve the yield of the reaction, all these are important for the consequent reactions. Two new 1,4-Dihydro-[1,2]dioxine-1,4-diols with seven-member-circularity 1,3,5-triene 92 and 101 were prepared by this method. Two 1,2-dialdehydes with seven-member-circularity 1,3,5-triene 91 and 100 as key intermediates of 92 and 101 were firstly prepared and discussed.
2. The optical pure isomers 39, 40, 95, 96, 104 and 105 of Shuangkangsu were successfully synthesized respectively from compound 1, 92, 101. The glucosylation methods for hydroxyl of substrate 1 was developed: The substrate 1 can be reacted with the alkyl thioglycoside donor by treat with N-Iodosuccinimide and Silver Trifluoromethanesulfonate, be reacted with the glycosyl trichloroacetimidate donor by treat with boron trifluoride ether complex or be reacted with the glycosyl trichloroacetimidate donor catalyzed by trimethylsilyl triflate (TMSOTf) to produce compounds 37 and 38 (optical pure isomers). The methods for removing the acetyl protective group in 3,6-O-glycosyl-[1,2]dioxane was also studied. Dibutyltin oxide was the proper reagent to remove the acetyl protective group in compounds 37, 38, 93, 94, 102 and 103. By comparing the CD spectra of compounds 39, 40, 95, 96, 104 and 105 with 6, 7 and/or Shuangkangsu of which the absolute configurations were specific, the absolute configuration of 39,40, 95, 96,104 and 105 were determined to (1R, 4R), (1S, 4S), (1R, 4R) and (1S, 4S). Some reactions' mechanisms were discussed.
3. Some analogs of Shuangkangsu and some intermediates were tested for antiviral activities and antitumor activities, the structure-activity relationship (SAR) and antiviral mechanism of this kind of compounds were also discussed.
4. The decomposition mechanisms of the peroxides under acidic or basic conditions were further discussed.
5. The synthesis of 1,3,5-triene was further studied and a new method to prepare (2Z, 4Z, 6Z)-diethyloxepine-4, 5-dicarboxylate just by one-step was disclosed. Synthesis of two alkyl-substituted analogues, an alky-/acyl-substitute analogue and some 1H-azepine analogues are also described. The property of this kind of reaction is firstly discussed in detail as followed.
6. In this work, 121 compounds including 41 new ones were synthesized. Among these compounds, 22 including 15 new ones are peroxides and 99 including 26 new ones are other types of compounds. And 17 of the peroxides are optical pure isomers including 10 new ones.
本课题从双抗素及其类似物的全合成研究入手,在本课题组已有的工作基础上发展了双抗素类分子中过氧键环系的合成方法,进一步研究了该类环状过氧半缩醛羟基的稳定性及有关反应活性,探索了该类化合物糖苷化以及糖基脱保护的方法,深入研究了三烯的合成,合成了双抗素结构类似物和简化物并对其进行了体外活性评价(包括抗病毒作用和抗肿瘤作用两方面),对实验中发现的新方法的适用性及有关反应特性进行了较为系统的研究。
主要完成了如下研究工作:
一、发展了双抗素类分子中过氧键环系的形成方法,即直接采用过氧化氢的水溶液在较低温度下对邻苯二甲醛进行分子内加成形成环过氧二半缩醛,简化了后处理,提高了产率,为后续反应提供更为充足的原料。用同样方法合成了含氧七员环状共轭三烯并环过氧二半缩醛化合物92和101,首次对其前体含氧七员环状共轭三烯邻二甲醛91和100的合成做了较为系统的研究并对其反应过程做了初步的探讨。
二、以化合物1为底物,结合本课题组已有的相关工作积累,进一步研究了双抗素类分子中环过氧化二半缩醛羟基的稳定性及有关反应活性,探索了该类化合物的糖苷化和脱乙酰保护基的方法,以硫苷为糖供体、NIS/AgOTf为催化剂的方法,三氯亚胺酯糖苷为糖供体、三氟化硼乙醚或者三甲基硅基三氟甲磺酸银为催化剂在低温无水无氧条件下对化合物1进行糖苷化反应,是比较适宜的方法。对过氧二半缩醛糖苷的脱乙酰保护基的方法也做了探索,发现二丁基氧化锡是37,38,93,94,102和103脱乙酰保护基的较为适宜的方法。按上述方法,分别以化合物1、92和101为底物,合成了光活纯的双抗素类似物39,40,95,96,104和105,其绝对构型通过与绝对构型已知的化合物6,7及双抗素分子进行有关CD谱比较的方法加以确定。对本课题有关的一些反应的机理作了初步探讨。
三、合成了双抗素类分子的系列简化物,对所合成的双抗素类似物和简化物进行了抗流感病毒和抗肿瘤活性筛选,并对其构效关系和作用机理进行了初步探讨。
四、进一步研究了在酸、碱或加热条件下,该类过氧化物中过氧键断裂的机理。
五、深入研究了共轭三烯片段的合成,发现了一步合成某些含氧或含氮杂原子的七员环共轭三烯邻二甲酸酯类化合物的新方法,首次较为系统地研究了其适用性和相关的反应特性。
Shuangkangsu, a new component with an unusual 1,2-dioxine skeleton first isolated by our group from a TCM (traditional Chinese medicine) named Jinyinhua, has a significant activity of inhibition of influenza virus in chicken embryo and respiratory syncytial virus in cells. The particular skeleton of the leading compound is valuable for new drug research and development.
For studying the total synthesis of Shuangkangsu and its analogs, in this work, the methods for the formation and glucosylation of 1,4-Dihydro-[1,2]dioxine-1,4-diol as well as the method for removal of acetyl protective group in compounds 37, 38 have been studied. Synthesis of 1,3,5-triene had been further studied and analogs of Shuangkangsu were synthesized before tested for bioactivities including antiviral activitives and antitumor activities in vitro. Meanwhile, some new synthetic methods have been found and some of the related reactions in this work have also been studied.
1. The ameliorative method for the formation of 1,4-Dihydro-[1,2]dioxine-1,4-diol, which is an intramolecular addition of hydrogen peroxide to 1,2-dialdehyde was established. This ameliorative method was used to simplify the procedure and improve the yield of the reaction, all these are important for the consequent reactions. Two new 1,4-Dihydro-[1,2]dioxine-1,4-diols with seven-member-circularity 1,3,5-triene 92 and 101 were prepared by this method. Two 1,2-dialdehydes with seven-member-circularity 1,3,5-triene 91 and 100 as key intermediates of 92 and 101 were firstly prepared and discussed.
2. The optical pure isomers 39, 40, 95, 96, 104 and 105 of Shuangkangsu were successfully synthesized respectively from compound 1, 92, 101. The glucosylation methods for hydroxyl of substrate 1 was developed: The substrate 1 can be reacted with the alkyl thioglycoside donor by treat with N-Iodosuccinimide and Silver Trifluoromethanesulfonate, be reacted with the glycosyl trichloroacetimidate donor by treat with boron trifluoride ether complex or be reacted with the glycosyl trichloroacetimidate donor catalyzed by trimethylsilyl triflate (TMSOTf) to produce compounds 37 and 38 (optical pure isomers). The methods for removing the acetyl protective group in 3,6-O-glycosyl-[1,2]dioxane was also studied. Dibutyltin oxide was the proper reagent to remove the acetyl protective group in compounds 37, 38, 93, 94, 102 and 103. By comparing the CD spectra of compounds 39, 40, 95, 96, 104 and 105 with 6, 7 and/or Shuangkangsu of which the absolute configurations were specific, the absolute configuration of 39,40, 95, 96,104 and 105 were determined to (1R, 4R), (1S, 4S), (1R, 4R) and (1S, 4S). Some reactions' mechanisms were discussed.
3. Some analogs of Shuangkangsu and some intermediates were tested for antiviral activities and antitumor activities, the structure-activity relationship (SAR) and antiviral mechanism of this kind of compounds were also discussed.
4. The decomposition mechanisms of the peroxides under acidic or basic conditions were further discussed.
5. The synthesis of 1,3,5-triene was further studied and a new method to prepare (2Z, 4Z, 6Z)-diethyloxepine-4, 5-dicarboxylate just by one-step was disclosed. Synthesis of two alkyl-substituted analogues, an alky-/acyl-substitute analogue and some 1H-azepine analogues are also described. The property of this kind of reaction is firstly discussed in detail as followed.
6. In this work, 121 compounds including 41 new ones were synthesized. Among these compounds, 22 including 15 new ones are peroxides and 99 including 26 new ones are other types of compounds. And 17 of the peroxides are optical pure isomers including 10 new ones.
引文
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