methyl 3,5-O-di-t-butylsilylene-α-D-arabinofuranoside | 232944-88-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl 3,5-O-di-t-butylsilylene-α-D-arabinofuranoside
• 英文别名: methyl 3,5-O-(di-tert-butylsilylene)-α-D-arabinofuranoside；(4aR,6S,7S,7aS)-2,2-ditert-butyl-6-methoxy-4a,6,7,7a-tetrahydro-4H-furo[3,2-d][1,3,2]dioxasilin-7-ol
• CAS: 232944-88-6
• 化学式: C₁₄H₂₈O₅Si
• 分子量: 304.459
• InChiKey: MUQCGSWKHGFABE-KXNHARMFSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.18
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 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：

  methyl 3,5-O-di-t-butylsilylene-α-D-arabinofuranoside 在 sodium hydroxide 、 9-borabicyclo[3.3.1]nonane dimer 、 四丁基氟化铵 、 sodium hydride 、 溶剂黄146 、 二甲基亚砜 、 N,N'-二环己基碳二亚胺 、 三氟乙酸 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 吡啶 、 乙醚 、 水 为溶剂， 反应 188.75h， 生成
  参考文献：
  名称：

  Conformationally Locked Nucleoside Analogs. Synthesis of 2′-Deoxy-2′-C, 4′-C-Bridged Bicyclic Nucleosides

  摘要：

  1-alpha-Methylarabinose was converted, in three steps, to 2-deoxy-2-methyleneribose derivative 3, which was subjected to hydroboration to give 2-alpha-hydroxymethyl derivative 4 exclusively; 4 was converted to 2,4-bis(hydroxymethyl)ribose derivative 6 in four steps. Mesylation, detritylation, and ring closure, followed by hydrolysis of the mesyl group at O5, gave 3,6-dioxabicyclo[3,2,1]octane derivative 8. After acetylation, 8 was coupled with silylated 6-chloropurine to give desired alpha- and beta-bicyclic-sugar nucleosides.

  DOI：

  10.1080/15257779908041488
• 作为产物：
  描述：

  二叔丁基硅基双(三氟甲烷磺酸) 、 methyl D-arabinofuranoside 在 2,6-二甲基吡啶 作用下， 以 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 4.0h， 以84%的产率得到methyl 3,5-O-di-t-butylsilylene-α-D-arabinofuranoside
  参考文献：
  名称：

  分枝杆菌阿拉伯半乳聚糖中的半乳糖胺残基是α-连接的

  摘要：

  先前的研究表明，来自分枝杆菌的细胞壁阿拉伯半乳聚糖具有单个半乳糖胺（GalN）残基。该部分是在氮上缺乏乙酰基的半乳糖胺的罕见天然存在之一，已被鉴定为连接到阿拉伯聚糖核心中高度分支的阿拉伯呋喃糖残基的侧基取代基。然而，GalN残基与多糖连接的立体化学仍然未知。我们在这里报告了两种四糖1和2的合成，由通过α-或β-键连接到分枝杆菌阿拉伯聚糖的三糖片段上的GalN组成。这些分子代表了第一个合成的含GalN寡糖，并且通过调节反应溶剂从单一供体物种实现了两个靶标的制备。将1和2的NMR光谱与从天然聚糖衍生的样品获得的NMR光谱进行比较，发现多糖中的GalN残基通过α键连接。

  DOI：

  10.1021/jo301393s

文献信息

• The Galactosamine Residue in Mycobacterial Arabinogalactan Is α-Linked
  作者：Wenjie Peng、Lu Zou、Suresh Bhamidi、Michael R. McNeil、Todd L. Lowary

  DOI：10.1021/jo301393s

  日期：2012.11.2

  This moiety, which is one of the rare natural occurrences of galactosamine lacking an acetyl group on the nitrogen, has been identified as a pendant substituent attached to a highly branched arabinofuranose residue in the arabinan core. However, the stereochemistry by which the GalN residue is linked to the polysaccharide remains unknown. We report here the synthesis of two tetrasaccharides, 1 and

  先前的研究表明，来自分枝杆菌的细胞壁阿拉伯半乳聚糖具有单个半乳糖胺（GalN）残基。该部分是在氮上缺乏乙酰基的半乳糖胺的罕见天然存在之一，已被鉴定为连接到阿拉伯聚糖核心中高度分支的阿拉伯呋喃糖残基的侧基取代基。然而，GalN残基与多糖连接的立体化学仍然未知。我们在这里报告了两种四糖1和2的合成，由通过α-或β-键连接到分枝杆菌阿拉伯聚糖的三糖片段上的GalN组成。这些分子代表了第一个合成的含GalN寡糖，并且通过调节反应溶剂从单一供体物种实现了两个靶标的制备。将1和2的NMR光谱与从天然聚糖衍生的样品获得的NMR光谱进行比较，发现多糖中的GalN残基通过α键连接。
• The use of O-trifluoroacetyl protection and profound influence of the nature of glycosyl acceptor in benzyl-free arabinofuranosylation
  作者：Polina I. Abronina、Ksenia G. Fedina、Nikita M. Podvalnyy、Alexander I. Zinin、Alexander O. Chizhov、Nikolay N. Kondakov、Vladimir I. Torgov、Leonid O. Kononov

  DOI：10.1016/j.carres.2014.05.017

  日期：2014.9

  The influence of O-trifluoroacetyl (TFA) groups at different positions of thioglycoside glycosyl donors on stereoselectivity of α-arabinofuranosylation leading to corresponding disaccharides was studied. It was shown that TFA group in thioglycoside glycosyl donors, when combined with 2-O-(triisopropylsilyl) (TIPS) non-participating group, may be regarded as an electron-withdrawing protecting group that may enhance 1,2-cis-selectivity in arabinofuranosylation, the results strongly depending on the nature of glycosyl acceptor. The reactivities of the glycosyl donors were compared with those of a similar thioglycoside with O-pentafluoropropionyl groups and the known phenyl 3,5-O-(di-tert-butylsilylene)-1-thio-α-d-arabinofuranosides with 2-O-TIPS and 2-O-benzyl groups. The 'matching' in the donor-acceptor combination was found to be critical for achieving both high reactivity of glycosyl donor and β-stereoselectivity of arabinofuranosylation. The use of glycosyl donors with TFA and silyl protection may be useful in the realization of the benzyl-free approach to oligoarabinofuranosides with azido group in aglycon-convenient building blocks for the preparation of neoglycoconjugates.
• Conformationally Locked Nucleoside Analogs. Synthesis of 2′-Deoxy-2′-C, 4′-C-Bridged Bicyclic Nucleosides
  作者：Guangyi Wang、Esmir Gunic

  DOI：10.1080/15257779908041488

  日期：1999.4

  1-alpha-Methylarabinose was converted, in three steps, to 2-deoxy-2-methyleneribose derivative 3, which was subjected to hydroboration to give 2-alpha-hydroxymethyl derivative 4 exclusively; 4 was converted to 2,4-bis(hydroxymethyl)ribose derivative 6 in four steps. Mesylation, detritylation, and ring closure, followed by hydrolysis of the mesyl group at O5, gave 3,6-dioxabicyclo[3,2,1]octane derivative 8. After acetylation, 8 was coupled with silylated 6-chloropurine to give desired alpha- and beta-bicyclic-sugar nucleosides.