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对烯丙基作为核苷糖环上羟基保护基进行了研究.烯丙基可用于核糖羟基的保护,用PdCl2可脱除核苷糖环上烯丙基,保护及脱保护都很简便.PdCl2还可脱除核苷糖环5'-OH常用的保护基--对甲氧基三苯甲基及二对甲氧基三苯甲基.控制适当的条件,PdCl2既能够选择性地脱除对甲氧基三苯甲基或二对甲氧基三苯甲基,又可同时脱除保护糖环羟基的烯丙基. 相似文献
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有机硅化合物在α-D-葡二糖合成上的应用 总被引:2,自引:0,他引:2
三苯基硅基作为葡萄糖1-C位羟基保护基, 在对硝基苯甲酰基存在下形成和脱保护基反应均易进行, 而且有产率高、在反应过程中保持1-C构型不变等特点, 并研究了三苯基硅基保护基在葡二糖上的应用。 相似文献
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近几年来, RNA的化学合成有了较大进展, 本文讨论了RNA化学合成过程中的保护基问题,着重介绍了核糖核苷的2'-和3'-位羟基的选择性保护方法。 相似文献
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羟基保护是糖化学合成的重要组成部分,羟基选择性部分保护的糖类衍生物中间体的合成往往需要多步反应或使用特殊试剂。本文以不同的甲基O-叔丁基二甲硅基糖苷为起始物,探讨了利用碱性条件下的硅基迁移反应合成选择性保护的糖类衍生物中间体的方法。例如,甲基6-O-叔丁基二甲硅基a-D-吡喃葡萄糖苷在NaH及BnBr 作用下进行苄基化反应,随后在酸性条件下脱去硅基,主要得到6-O→4-O硅基迁移的产物,甲基2,3,6-三-O-苄基a-D-吡喃葡萄糖苷。提出了一种简便合成选择性苄基保护的甲基2,3,6-三-O-苄基a-D-吡喃葡萄糖苷的有效方法。 相似文献
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碳苷研究 V: 用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护 总被引:1,自引:0,他引:1
本文报道了一些取代苯酚的合成, 并探讨了用Grignard试剂合成取代苯酚中酚羟基的保护及脱保护的问题. 利用苄基和甲基作为酚羟基的保护基, 对文献报道的切断醚键脱保护方法进行了评价. 找到了两种新体系能在更温和条件下切断醚键的方法, 指出了它们的适用条件. 实验结果符合硬软酸碱理论. 相似文献
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一种中性条件下脱除THP保护基的简易方法 总被引:1,自引:0,他引:1
四氢吡喃醚(THP)是一种常用的保护基,在有机合成中被广泛地用于羟基的保护。它的脱除通常采用强酸(如三氟乙酸等)条件下进行。近来,曾报道了一些在弱酸性条件下脱除THP保护基的方法。我们利用Me_3SiCl/NaI在中性条件下有效地脱除了THP保护基,见式1。 相似文献
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三苯基硅基作为葡萄糖1-C位羟基保护基,在对硝基苯甲酰基存在下形成和脱保护基反应均易进行,而且有产率高、在反应过程中保持1-C构型不变等特点。并研究了三苯基硅基保护基在葡二糖上的应用。 相似文献
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Modification of carbohydrates and their analogs is hindered due to multi-step synthetic methodologies involving selective protection and deprotection of multiple hydroxyl groups present in the molecule. A highly efficient route for the synthesis of 1-phenyl-2-(β-D-glycopyranosyl)ethenes has been developed from native sugars, which neither requires protection/deprotection of the hydroxyl groups nor use of any metal/metal ions. The key step of the developed methodology is the use of Bamford-Stevens reaction which led to the formation of the desired compounds in moderate to high yields in three steps only. 相似文献
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Selective phosphitylation of the primary hydroxyl group in unprotected carbohydrates and nucleosides
[reaction: see text] Carbohydrates and nucleosides containing a phosphate at the less-hindered primary hydroxyl group are often prepared using a protection/deprotection strategy. Herein we report that the phosphoramidite method can be used to selectively incorporate phosphorus at the primary hydroxyl group of O-unprotected carbohydrates and nucleosides; in situ oxidation of the resulting phosphite triester yields the phosphate triester. 相似文献
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Han Wang Renyang Xu Shuobin Liang Fuxiang Ran Lihe Zhang Yongmin Zhang Demin Zhou Sulong Xiao 《中国化学快报》2020,31(2):333-336
The acetyl ester plays an important role for protection of the hydroxyl groups in carbohydrates synthesis.In the present study,we described an efficient deprotection of acetyl group of pentacyclic triterpenoid by using methanolic ammonia in THF solution.Good selectivity for cleaving gal-C2-OAc group of 3β-hydroxy-olean-12-en-28-oic acid 28-N-2,3,4,6-tetra-O-acetyl-β-D-galactopyranoside(3) was achieved in the presence of methanolic ammonia within 4 h at low temperature(-60℃) in a yield of 56%.The reaction disclosed here provides a new method for the synthesis of C2 selective modified carbohydrates,which is more useful than conventional synthesis procedure that usually requires many steps including temporary regioselective protection and deprotection.When the reaction temperature was increased from -60℃ to room temperature,the cleavage of the other three acetyl groups of galactose in an order of C4-OAc>C3-OAc>C6-OAc was observed.Based on this study,a plausible route for the deacetylation reaction has been proposed. 相似文献
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Y. C. Lee 《Journal of chromatography. A》1996,720(1-2):137-149
High-performance anion-exchange chromatography (HPAEC), in tandem with pulsed amperometric detector (PAD) is a powerful tool for carbohydrate analysis. It requires no pre- or postcolumn derivatization, and yet offers superb resolution and sensitiviy. In its basic mode, alcoxide anions from the hydroxyl groups of carbohydrates as well as other anionic substituents are utilized. In addition to the number of hydroxyl groups, separation can be based on anomers, positional isomers, as well as degree of polymerization. 相似文献
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Pulsed amperometric detection of calystegines separated by capillary electrophoresis 总被引:1,自引:0,他引:1
Calystegines are polyhydroxyalkaloids with a nortropane skeleton. They are oxidized by pulsed amperometry at a gold electrode due to their vicinal hydroxyl groups similar to monosaccharides, but at a slightly higher potential. Compared to carbohydrates, calystegines exhibit lower acidity, thus the effective electrophoretic mobility as anions in 0.1 M NaOH is lower, independent of their molecular mass. The acidity and mobility of calystegines increase with the number of hydroxyl groups. The influence of temperature and power dissipation in the capillary and changes of the inner surface on the migration times was eliminated by cooling and subtraction of the electroosmotic flow velocity. The high resolving power of capillary zone electrophoresis allows the separation of calystegines with the same number of hydroxyl groups. Detection is linear from 2 to 200 mg L(-1) with a 1 nL injection volume. Calystegines were determined in crude plant sap after filtration without further sample purification. 相似文献
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A method for enumerating hydroxyl groups in analytes is described and applied to various carbohydrates. The analytes were derivatized in solution by using trimethylsilylimidazole (TMSI) and the products were analyzed without chromatography by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The mass spectra revealed consecutive product ion peaks that are separated by 72 m/z units. This 72 m/z unit separation is a result of displacement of a hydroxyl hydrogen atom by a trimethylsilyl group. The number of the observed ions was used to confirm the number of hydroxyl groups in each analyte. This method was utilized in the analysis of single and multi-component analytes. 相似文献
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Peter J. Card 《Journal of carbohydrate chemistry》2013,32(4):451-487
The similarities in bond length and polarization between C-F and C-OH, as well as the altered hydrogen-bonding properties present in carbohydrates bearing a fluorine atom in place of an hydroxyl group can be exploited in place of an hydroxyl group can be exploited in biochemical investigations (enzyme-carbohydrate interactions, Lectin-carbohydrate affinities, antiobody-carbohydrate binding, etc.). 1–5 In addition, the different chemistries exhibited by the flourinated carbohydrates have made them important reagents in both metabolic studies and disease diagnosis such as the use of 2-deoxy-2-[18f]-D-fluoroglucose in positron emission tomography. 6,7 Becasue of their widespread utlity, the synthesis of fluorinated carbohydrates is of importance. However, the Introduction of fluorine into a carbohydrate moiety can be an arduous task because of (1) the protection and deprotection steps required to set up the desired hydroxyl group for the introduction of fluoride, (2) the low nucleophilicity fo fluoride ion, and (3) fluoride ion catalyzed elimination reactions. 8,9 The search for Milder and more selective methods for the introduction of fluorine into Carbohydrates has continued at a rapid pace and it is appropriate to review som of the recent results. 相似文献