(3aR,5S,6S,6aR)-5-{[(tert-butyldiphenylsilyl)oxy]methyl}-2,2-dimethyltetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol | 103763-14-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3aR,5S,6S,6aR)-5-{[(tert-butyldiphenylsilyl)oxy]methyl}-2,2-dimethyltetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol
• 英文别名: 5-O-tert-butyldiphenylsilyl-1,2-O-(1-methylethylidene)-β-L-arabinofuranose；1,2-O-isopropylidene-5-O-(tert-butyldiphenylsilyl)-β-L-arabinofuranose；5-O-(tert-butyldiphenylsilyl)-1,2-O-isopropylidene-β-L-arabinofuranose；5-O-tert-butyldiphenylsilyl-1,2-O-isopropylidene-β-L-arabinofuranose；5-O-tert-butyldiphenylsilyl-1,2-isopropylidene-β-L-arabinofuranose；5-O-t-butyldiphenylsilyl-1,2-O-isopropylidene-β-L-arabinofuranose；5-O-tert-Butyldiphenylsilyl-1,2-O-isopropylidene-beta-L-arabinofuranose；(3aR,5S,6S,6aR)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]-2,2-dimethyl-3a,5,6,6a-tetrahydrofuro[2,3-d][1,3]dioxol-6-ol
• CAS: 103763-14-0
• 化学式: C₂₄H₃₂O₅Si
• 分子量: 428.601
• InChiKey: XJKAZNSYWAGYDQ-FNAHDJPLSA-N

物化性质

• 沸点：
  495.5±45.0 °C(Predicted)
• 密度：
  1.16±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  30
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  57.2
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (3aR,5S,6S,6aR)-5-{[(tert-butyldiphenylsilyl)oxy]methyl}-2,2-dimethyltetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol 在 四氯化碳 、 4-二甲氨基吡啶 、 磷酸酐 、 sodium tetrahydroborate 、 sodium periodate 、 偶氮二异丁腈 、 三正丁基氢锡 、 溶剂黄146 、 三苯基膦 作用下， 以 甲苯 、 乙腈 为溶剂， 反应 56.08h， 生成 (R)-1-((tert-butyldiphenylsilyl)oxy)-4-chloro-2-(methoxymethoxy)butane
  参考文献：
  名称：

  An Enantiospecific Synthesis of the Human Cytomegalovirus Antiviral Agent [(R)-3-((2-Amino-1,6-dihydro-6-oxo-9H-purin-9-yl)methoxy)-4- hydroxybutyl]phosphonic Acid

  摘要：

  The racemic isosteric phosphonate of ganciclovir monophosphate (BW2482U89, SR3745, [3-((2-amino-1,6-dihydro-6-oxo-9H-purin-9-yl)methoxy)-4-hydroxybutyl]phosphonic acid, 1) has potent and selective in vitro;activity against human cytomegalovirus. An enantiospecific synthesis of the R-enantiomer of compound 1 starting from L-arabinose was developed. The synthesis involved (1) the preparation of a chiral acyclic moiety, (2) the coupling of the chiral acyclic moiety to diacetylguanine, (3) the introduction; of phosphorus, and (4) the final deprotection. The R-enantiomer, which has stereochemistry analogous to the natural compound GMP, was tested against human cytomegalovirus and had an IC50 Of 1.7 mu M, which was approximately 2-fold more active than the racemic material. Both racemic and chiral compounds were less toxic than ganciclovir to bone marrow progenitor cells in an in vitro assay.

  DOI：

  10.1021/jm00035a018
• 作为产物：
  描述：

  L-(+)-arabinose 在 硫酸 咪唑 、 copper(II) sulfate 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 (3aR,5S,6S,6aR)-5-{[(tert-butyldiphenylsilyl)oxy]methyl}-2,2-dimethyltetrahydro-2H-furo[2,3-d][1,3]dioxol-6-ol
  参考文献：
  名称：

  [EN] BICYCLIC NUCLEOSIDES AND OLIGOMERIC COMPOUNDS PREPARED THEREFROM
  [FR] NUCLÉOSIDES BICYCLIQUES ET COMPOSÉS OLIGOMÈRES ÉLABORÉS À PARTIR DE CES NUCLÉOSIDES

  摘要：

  本发明提供了新颖的3'，5'-连接的双环核苷和由此制备的寡聚化合物。本文提供的双环核苷可用于增强其所结合到的寡聚化合物的一个或多个性质，如核酸酶抗性。

  公开号：

  WO2011156278A1

文献信息

• 2'-deoxy-L-nucleosides
  申请人：Watanabe Kyoichi

  公开号：US20050090660A1

  公开（公告）日：2005-04-28

  This invention provides processes for the preparation of compounds having the structure: wherein X and Y are same or different, and H, OH, OR, SH, SR, NH 2 , NHR′, or NR′R″ Z is H, F, Cl, Br, I, CN, or NH 2 . R is hydrogen, halogen, lower alkyl of C 1 -C 6 or aralkyl, NO 2 , NH 2 , NHR′, NR′R″, OH, OR, SH, SR, CN, CONH 2 , CSNH 2 , CO 2 H, CO 2 R′, CH 2 CO 2 H, CH 2 CO 2 R′, CH═CHR, CH 2 CH═CHR, or C═CR. R′ and R″ are same or different, and lower alkyl of C 1 -C 6 . R 13 is hydrogen, alkyl, acyl, phosphate (monophosphate, diphosphate, triphosphate, or stabilized phosphate) or silyl; and

  这项发明提供了制备具有以下结构的化合物的方法： 其中 X和Y相同或不同，且H、OH、OR、SH、SR、NH2、NHR′或NR′R″ Z为H、F、Cl、Br、I、CN或NH2 R为氢、卤素、C1-C6的低碳烷基或芳基烷基、NO2、NH2、NHR′、NR′R″、OH、OR、SH、SR、CN、CONH2、CSNH2、CO2H、CO2R′、CH2CO2H、CH2CO2R′、CH═CHR、CH2CH═CHR或C═CR。 R′和R″相同或不同，且为C1-C6的低碳烷基。 R13为氢、烷基、酰基、磷酸酯（单磷酸酯、二磷酸酯、三磷酸酯或稳定磷酸酯）或硅基。
• An eco-compatible strategy for the diversity-oriented synthesis of macrocycles exploiting carbohydrate-derived building blocks
  作者：Sushil K Maurya、Rohit Rana

  DOI：10.3762/bjoc.13.110

  日期：——

  An efficient, eco-compatible diversity-oriented synthesis (DOS) approach for the generation of library of sugar embedded macrocyclic compounds with various ring size containing 1,2,3-triazole has been developed. This concise strategy involves the iterative use of readily available sugar-derived alkyne/azide-alkene building blocks coupled through copper catalyzed azide-alkyne cycloaddition (CuAAC) reaction

  已经开发出一种有效的，生态相容的，面向多样性的合成（DOS）方法，用于生成包含各种环大小的含1,2,3-三唑的糖嵌入大环化合物的文库。这种简洁的策略涉及通过铜催化的叠氮化物-炔烃环加成（CuAAC）反应偶联使用容易获得的糖衍生的炔烃/叠氮化物-烯烃构件，然后使用更绿色的反应条件配对线性环加合物。生态相容性，温和的反应条件，较绿色的溶剂，易于纯化的方法以及避免危害和有毒溶剂的使用是该方案进入这一重要结构类别的优势。
• Synthesis of <i>cis</i>- and <i>trans</i>-α-<scp>l</scp>-[4.3.0]Bicyclo-DNA Monomers for Antisense Technology: Methods for the Diastereoselective Formation of Bicyclic Nucleosides
  作者：Stephen Hanessian、Benjamin R. Schroeder、Bradley L. Merner、Bin Chen、Eric E. Swayze、Punit P. Seth

  DOI：10.1021/jo401166q

  日期：2013.9.20

  reaction to a carbohydrate system. In the case of analogue 13, where a trans-ring junction was desired, an intermolecular diastereoselective Grignard reaction followed by ring-closing metathesis was used. In order to set the desired stereochemistry at the C5′ positions of both nucleoside targets, a study of diastereoselective Lewis acid mediated allylation reactions on a common bicyclic aldehyde precursor

  两个α-升-核糖-构型的双环核酸修饰，由类似物表示12和13，其是位于C差向异构体3 '和C 5 '已使用基于碳水化合物的方法来构建双环核心结构合成。分子内1-脯氨酸介导的羟醛反应被用于产生类似物12的顺式构型的环连接，并且代表了这种古老的有机催化反应在碳水化合物体系中的罕见应用。在模拟的情况下13，其中一个反需要一个环状连接，使用分子间非对映选择性格氏反应，然后进行闭环复分解。为了将期望的立体化学设置在两个核苷靶的C 5 '位置，进行了对非对映选择性路易斯酸介导的对常见双环醛前体的烯丙基化反应的研究。类似物12被掺入寡核苷酸序列中，并且热变性实验表明，当与互补的DNA和RNA配对时，它是不稳定的。但是，该构建体相对于DNA寡核苷酸显示出核酸酶稳定性的显着改善。
• Free radical 5-exo-dig cyclization as the key step in the synthesis of bis-butyrolactone natural products: experimental and theoretical studies
  作者：Gangavaram V. M. Sharma、Devoju Harinada Chary、Nagula Chandramouli、Florian Achrainer、Sateesh Patrudu、Hendrik Zipse

  DOI：10.1039/c1ob00019e

  日期：——

  Radical cyclization reactions were performed by 5-exo-dig mode to yield cis-fused bicyclic systems, leading to the synthesis of bis-butyrolactone class of natural products. The study was aimed at understanding the impact of alkyl side chains of furanoside ring systems in L-ara configuration on the radical cyclization. It was amply demonstrated by experimental studies that the increase in the length of the alkyl side chain has an effect on the cyclization: while efficient cyclization reactions could be realized with methyl and ethyl side chains, the yields were significantly reduced in the case of n-pentyl side chain. Theoretical studies using DFT and (RO)MP2 methods were carried out to analyze the influence of the substitution pattern on the cyclization barriers.

  采用5-exo-dig模式进行自由基环化反应，以获得顺式融合的双环系统，从而合成了双丁内酯类自然产物。本研究旨在了解L-ara构型的呋喃苷环系统中的烷基侧链对自由基环化反应的影响。实验研究充分表明，烷基侧链长度的增加对环化反应有影响：在甲基和乙基侧链的情况下可以实现高效的环化反应，而在正戊基侧链的情况下，产率显著降低。使用DFT和(RO)MP2方法进行了理论研究，以分析取代模式对环化势垒的影响。
• Synthesis of spiro carbon linked disaccharides from d-glucose, d- and l-arabinose
  作者：G.V.M Sharma、V.Goverdhan Reddy、Palakodety Radha Krishna、A.Ravi Sankar、A.C Kunwar

  DOI：10.1016/s0040-4020(02)00319-8

  日期：2002.5

  The synthesis of new spiro carbon linked disaccharides from d-glucose, d- and l-arabinose is described. In the present study furan is used as a masked sugar synthon, while chirality is transferred from the sugar derived chiral templates.

  描述了由d-葡萄糖，d-和1-阿拉伯糖合成新的螺碳连接的二糖。在本研究中，呋喃用作掩蔽的糖合成子，而手性则从糖衍生的手性模板转移而来。