负载金属钌卟啉、BINOL及其衍生物诱导的不对称反应研究及N_2S_2型化合物与DNA相互作用研究
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摘要
金属卟啉配合物能有效地、高产率、高选择性地催化简单烯烃环氧化，但催化剂稳定性差，重复使用困难。负载的金属卟啉克服了这一难题，并已经广泛用于绝大多数烯烃的催化环氧化，但用于对天然化合物的环氧化则不多。本文成功设计并合成了无机载体(3-氨基丙基硅胶(APS))负载五氟苯基钌卟啉[APS-Ru(Ⅱ)(tfpp)CO]，并对该负载的金属卟啉进行了详细的表征。
5B，6B-甾族环氧化物是合成其它甾族化合物的重要中间体。由于C-10上的B-甲基的影响，通常的环氧化方法只得到以a-环氧化物为主的混合物。本文以3-氨基丙基硅胶(APS)负载的五氟苯基钌卟啉[APS-Ru(Ⅱ)(tfpp)CO]为催化剂，成功用于不饱和甾族环氧化反应，并取得比较好的结果：(1)催化△~5-甾族衍生物环氧化，高转化率(100％)、高产率(97％)、高选择性(99％)地获得了B-环氧化物，而五氟苯基钌卟啉催化只得到了81％的B-选择性。(2)催化△~4-甾族衍生物环氧化，虽然产率相对比较低，但也能得到99％的B-选择性。(3)负载后的五氟苯基钌卟啉表现出了高的稳定性。重复使用五次后，其催化活性没有明显下降，催化乙酰胆固醇环氧化仍能得到93％的产率和92％的B-选择性。(4)反应产物比较单一，后处理简单，过滤就能回收催化剂，滤液除去溶剂，干燥后，直接加入标样利用核磁分析得到催化反应的转化率、产率和选择性。(5)分析方法简单，反应过程达到了绿色化的要求。
N_2S_2配体由于其特殊的结构，已在配位化学、放射性元素的标记、放射性诊断和治疗以及放射性药物的合成等方面得到广泛的应用和发展。本文成功设计并合成了N_2S_2配体哌啶衍生物NEPDDD、NEMPDDD、NEMMPDDD、NNEPDD、NNEMPDD，并将三种单取代的哌啶衍生物NEPDDD、NEMPDDD、NEMMPDDD成功用于DNA的切割，获得了比较好的结果：(1)三种单取代的哌啶衍生物都能对超螺旋DNApUC19产生有效的切割作用而生成FormⅡ，其中，NEMPDDD的切割作用最强。(2)以NEMPDDD为例，研究了时间、浓度和pH值对切割作用的影响，结果表明：在37℃、pH=7.0的条件下，0.286mM的NEMPDDD能将超螺旋DNA(FormⅠ)在24h内完全转化为FormⅡ。(3)以NEMPDDD为例，对切割机理进行了初步的探索，结果发现，催化断裂DNA是按氧化途径进行的。(4)首次将N_2S_2自由配体用于DNA的切割实验，同金属人工核酸酶相比，N_2S_2配体哌啶衍生物自由配体同样具有人工核酸酶的作用。
Diels-Alder反应是有机化学中构建六员环和碳碳键形成最为重要的反应之一。其中，硅醚二烯与羰基化合物的不对称Hetero-Diels-Alder(HDA)反应合成光学活性的二氢吡喃酮衍生物的研究尤为引人注目。本文用简单的TICl_4和(R)-BINOL、以简单的醇钠为添加剂，成功催化了芳香醛与Trans-4-methoxy-2-trimethylsiloxy-penta-1,3-diene的不对称Hetero-Diels-Alder反应，获得一系列的研究成果：(1)通过对不同醇钠作为添加剂进行考察，结果发现：在0℃时，以仲丁醇钠作为添加剂，在CH_2Cl_2中反应48 h后，TiCl_4和(R)-BINOL能有效地催化对硝基苯甲醛与Trans-4-methoxy-2-trimethylsiloxy-penta-1,3-diene的不对称Hetero-Diels-Alder反应，并得到86％收率和94％的对映选择性。(2)通过实验证明，该催化体系也能成功催化其它芳香醛与二烯的HDA反应。(3)实验结果表明，芳香醛的取代基位置对反应的产率和选择性影响较大，取代基的电子效应对反应的产率和选择性影响较小。(4)成功找到了一种简单而有效的方法、高对映选择性地合成2，6-二取代二氢吡喃酮衍生物。
同时，我们又成功设计并合成了3-和3，3′-联萘酚咪唑长链烷基鎓盐。并探索了联萘酚咪唑长链烷基鎓盐在不对称催化反应中的应用。结果发现：在催化直接Aldol反应、azo-Diels-Alder反应、氧杂-Diels-Alder反应和苯甲酰甲酸乙酯的羟基化反应中，虽然没有得到我们所期望的结果，但体现了该类化合物仍然具有一定的催化活性。只要选择合适的反应，在一定的条件下，这种手性联萘酚咪唑长链烷基翁盐还是能在不对称催化合成中发挥应有的作用。
Metalloporphyrins have been applied to catalyze the epoxidation of unfunctionalized alkenes. In recent years emphasis has been put on the stability and reuse of the metalloporphyrins. Therefore, many supported metalloporphyrins have been synthesized with high stability. The ruthenium(Ⅱ) 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin(tfpp) carbonyl complex has been covalently attached to a 3-aminoporpyl functionalized silica gel(APS).
Steroid epoxides are an important class of oxysterols (derivatives of cholesterol) that regulate cell proliferation and cholesterol homeostasis in organism. They are also versatile intermediates for steroid synthesis, playing increasingly important roles in the biochemical studies of enzymes, this supported ruthenium porphyrin(APS-Ru(Ⅱ)(tfpp)CO) was applied to catalyze the epoxidation ofΔ~5- andΔ~4-unsaturated steroids, and the encouraging results are obtained. Firstly, the epoxidation ofΔ~5-steroids obtained high yield (up to 99%) andβ-selectivity(up to 99%). Secondly, this supported metalloporphyrin could also catalyzeΔ~4- steroids and the catalytic reactions obtained 99%β-selectivity, though the yields were low. Thirdly, this supported metalloporphyrin had high stability, and the activity didn't decrease after being reused five times. Finally, the analysis of the reaction results was simple by ~1H-NMR, and the catalyst can easily be reused.
Ligands with N_2S_2 structures, especially 2, 9- dimethyl-4, 7-diazadecane-2, 9-dithiol (DDD), have been studied in recent years. DDD is a strong chelating agent and can form stable lipophilic chelate complex with technetium or rhenium in high yields. The derivatives of N_2S_2 ligands have been employed in diagnostic imaging, radiopharmaceuticals, nuclear medicine and so on. Five N_2S_2 piperidine derivatives, NEPDDD, NEMPDDD, NEMMPDDD, NNEPDDD, NNEMPDDD, were synthesized. Three derivatives(NEPDDD, NEMPDDD, NEMMPDDD) were selected to catalyze DNA cleavage, and obtained a series of encouraging results. First, the three free ligands could cleave plasmid DNA(pUC 19) efficiently, especially NEMPDDD. Second, for the cleavage reaction catalyzed by NEMPDMDD, FormⅠDNA could convert to FormⅡcompletely in 24 h at 37℃under physiological condition(pH 7.0). Third, the DNA-cleavage mechanism involved an oxidative pathway. Eventually, the free N_2S_2 piperidine derivatives were employed in DNA cleavage for the first time. The results show that these free ligands have the same catalysis activity as restriction enzymes.
Diets-Alder reaction is one of the important reactions in organic chemistry for the construction of six-membered rings and the formation of carbon-carbon bonds. Asymmetric Hetero-Diets-Alder reaction (HDA) between electron-rich diene with aldehydes can provide a series of dihydropyrans and dihydropyranones which are among the most important intermediates in the synthesis of many natural products. The Hetero-Diels-Alder reactions of trans-4-methoxy-2-trimethylsiloxy-penta-1,3-diene with aromatic aldehyde were studied and the encouraging results were obtained. Firstly, optically active 2,6-disubstituted dihydropyrones were available by hetero-Diels-Alder (HDA) reaction of aldehydes and diene in presence of MCl_4 (M=Wi~(4+), Sn~(4+)) and (R)-BINOL with sodium alcoholates as additives under mild reaction conditions. Secondly, all the reaction products catalyzed by TiCl_4 and BINOL with NaOCH -(CH_3)CH_2CH_3 as an additive were obtained up to 88% yield and 94% ee. Finally, the substituent positions of aromatic ring affected the yield and enantioselectivity of HAD reactions, but the electric effects of substituent were not significant.
At the same time, the 3- and 3,3'-BINOL imidazonium were synthesized successfully, and were used to catalyze direct Aldol reaction, HDA reaction and the hydroacylation of a-keto ester with aldehyde. Although the catalytic reactions has no results, this imidazonium will be employed in some reaction under capable conditions.
5B，6B-甾族环氧化物是合成其它甾族化合物的重要中间体。由于C-10上的B-甲基的影响，通常的环氧化方法只得到以a-环氧化物为主的混合物。本文以3-氨基丙基硅胶(APS)负载的五氟苯基钌卟啉[APS-Ru(Ⅱ)(tfpp)CO]为催化剂，成功用于不饱和甾族环氧化反应，并取得比较好的结果：(1)催化△~5-甾族衍生物环氧化，高转化率(100％)、高产率(97％)、高选择性(99％)地获得了B-环氧化物，而五氟苯基钌卟啉催化只得到了81％的B-选择性。(2)催化△~4-甾族衍生物环氧化，虽然产率相对比较低，但也能得到99％的B-选择性。(3)负载后的五氟苯基钌卟啉表现出了高的稳定性。重复使用五次后，其催化活性没有明显下降，催化乙酰胆固醇环氧化仍能得到93％的产率和92％的B-选择性。(4)反应产物比较单一，后处理简单，过滤就能回收催化剂，滤液除去溶剂，干燥后，直接加入标样利用核磁分析得到催化反应的转化率、产率和选择性。(5)分析方法简单，反应过程达到了绿色化的要求。
N_2S_2配体由于其特殊的结构，已在配位化学、放射性元素的标记、放射性诊断和治疗以及放射性药物的合成等方面得到广泛的应用和发展。本文成功设计并合成了N_2S_2配体哌啶衍生物NEPDDD、NEMPDDD、NEMMPDDD、NNEPDD、NNEMPDD，并将三种单取代的哌啶衍生物NEPDDD、NEMPDDD、NEMMPDDD成功用于DNA的切割，获得了比较好的结果：(1)三种单取代的哌啶衍生物都能对超螺旋DNApUC19产生有效的切割作用而生成FormⅡ，其中，NEMPDDD的切割作用最强。(2)以NEMPDDD为例，研究了时间、浓度和pH值对切割作用的影响，结果表明：在37℃、pH=7.0的条件下，0.286mM的NEMPDDD能将超螺旋DNA(FormⅠ)在24h内完全转化为FormⅡ。(3)以NEMPDDD为例，对切割机理进行了初步的探索，结果发现，催化断裂DNA是按氧化途径进行的。(4)首次将N_2S_2自由配体用于DNA的切割实验，同金属人工核酸酶相比，N_2S_2配体哌啶衍生物自由配体同样具有人工核酸酶的作用。
Diels-Alder反应是有机化学中构建六员环和碳碳键形成最为重要的反应之一。其中，硅醚二烯与羰基化合物的不对称Hetero-Diels-Alder(HDA)反应合成光学活性的二氢吡喃酮衍生物的研究尤为引人注目。本文用简单的TICl_4和(R)-BINOL、以简单的醇钠为添加剂，成功催化了芳香醛与Trans-4-methoxy-2-trimethylsiloxy-penta-1,3-diene的不对称Hetero-Diels-Alder反应，获得一系列的研究成果：(1)通过对不同醇钠作为添加剂进行考察，结果发现：在0℃时，以仲丁醇钠作为添加剂，在CH_2Cl_2中反应48 h后，TiCl_4和(R)-BINOL能有效地催化对硝基苯甲醛与Trans-4-methoxy-2-trimethylsiloxy-penta-1,3-diene的不对称Hetero-Diels-Alder反应，并得到86％收率和94％的对映选择性。(2)通过实验证明，该催化体系也能成功催化其它芳香醛与二烯的HDA反应。(3)实验结果表明，芳香醛的取代基位置对反应的产率和选择性影响较大，取代基的电子效应对反应的产率和选择性影响较小。(4)成功找到了一种简单而有效的方法、高对映选择性地合成2，6-二取代二氢吡喃酮衍生物。
同时，我们又成功设计并合成了3-和3，3′-联萘酚咪唑长链烷基鎓盐。并探索了联萘酚咪唑长链烷基鎓盐在不对称催化反应中的应用。结果发现：在催化直接Aldol反应、azo-Diels-Alder反应、氧杂-Diels-Alder反应和苯甲酰甲酸乙酯的羟基化反应中，虽然没有得到我们所期望的结果，但体现了该类化合物仍然具有一定的催化活性。只要选择合适的反应，在一定的条件下，这种手性联萘酚咪唑长链烷基翁盐还是能在不对称催化合成中发挥应有的作用。
Metalloporphyrins have been applied to catalyze the epoxidation of unfunctionalized alkenes. In recent years emphasis has been put on the stability and reuse of the metalloporphyrins. Therefore, many supported metalloporphyrins have been synthesized with high stability. The ruthenium(Ⅱ) 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin(tfpp) carbonyl complex has been covalently attached to a 3-aminoporpyl functionalized silica gel(APS).
Steroid epoxides are an important class of oxysterols (derivatives of cholesterol) that regulate cell proliferation and cholesterol homeostasis in organism. They are also versatile intermediates for steroid synthesis, playing increasingly important roles in the biochemical studies of enzymes, this supported ruthenium porphyrin(APS-Ru(Ⅱ)(tfpp)CO) was applied to catalyze the epoxidation ofΔ~5- andΔ~4-unsaturated steroids, and the encouraging results are obtained. Firstly, the epoxidation ofΔ~5-steroids obtained high yield (up to 99%) andβ-selectivity(up to 99%). Secondly, this supported metalloporphyrin could also catalyzeΔ~4- steroids and the catalytic reactions obtained 99%β-selectivity, though the yields were low. Thirdly, this supported metalloporphyrin had high stability, and the activity didn't decrease after being reused five times. Finally, the analysis of the reaction results was simple by ~1H-NMR, and the catalyst can easily be reused.
Ligands with N_2S_2 structures, especially 2, 9- dimethyl-4, 7-diazadecane-2, 9-dithiol (DDD), have been studied in recent years. DDD is a strong chelating agent and can form stable lipophilic chelate complex with technetium or rhenium in high yields. The derivatives of N_2S_2 ligands have been employed in diagnostic imaging, radiopharmaceuticals, nuclear medicine and so on. Five N_2S_2 piperidine derivatives, NEPDDD, NEMPDDD, NEMMPDDD, NNEPDDD, NNEMPDDD, were synthesized. Three derivatives(NEPDDD, NEMPDDD, NEMMPDDD) were selected to catalyze DNA cleavage, and obtained a series of encouraging results. First, the three free ligands could cleave plasmid DNA(pUC 19) efficiently, especially NEMPDDD. Second, for the cleavage reaction catalyzed by NEMPDMDD, FormⅠDNA could convert to FormⅡcompletely in 24 h at 37℃under physiological condition(pH 7.0). Third, the DNA-cleavage mechanism involved an oxidative pathway. Eventually, the free N_2S_2 piperidine derivatives were employed in DNA cleavage for the first time. The results show that these free ligands have the same catalysis activity as restriction enzymes.
Diets-Alder reaction is one of the important reactions in organic chemistry for the construction of six-membered rings and the formation of carbon-carbon bonds. Asymmetric Hetero-Diets-Alder reaction (HDA) between electron-rich diene with aldehydes can provide a series of dihydropyrans and dihydropyranones which are among the most important intermediates in the synthesis of many natural products. The Hetero-Diels-Alder reactions of trans-4-methoxy-2-trimethylsiloxy-penta-1,3-diene with aromatic aldehyde were studied and the encouraging results were obtained. Firstly, optically active 2,6-disubstituted dihydropyrones were available by hetero-Diels-Alder (HDA) reaction of aldehydes and diene in presence of MCl_4 (M=Wi~(4+), Sn~(4+)) and (R)-BINOL with sodium alcoholates as additives under mild reaction conditions. Secondly, all the reaction products catalyzed by TiCl_4 and BINOL with NaOCH -(CH_3)CH_2CH_3 as an additive were obtained up to 88% yield and 94% ee. Finally, the substituent positions of aromatic ring affected the yield and enantioselectivity of HAD reactions, but the electric effects of substituent were not significant.
At the same time, the 3- and 3,3'-BINOL imidazonium were synthesized successfully, and were used to catalyze direct Aldol reaction, HDA reaction and the hydroacylation of a-keto ester with aldehyde. Although the catalytic reactions has no results, this imidazonium will be employed in some reaction under capable conditions.
引文
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