phenyl 2-O-triisopropylsilyl-3,5-di-O-trifluoroacetyl-1-thio-α-D-arabinofuranoside | 1621691-58-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: phenyl 2-O-triisopropylsilyl-3,5-di-O-trifluoroacetyl-1-thio-α-D-arabinofuranoside
• CAS: 1621691-58-4
• 化学式: C₂₄H₃₂F₆O₆SSi
• 分子量: 590.656
• InChiKey: BILCYEJJBRASJC-YSTOQKLRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.64
• 重原子数：
  38.0
• 可旋转键数：
  10.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  phenyl 2-O-triisopropylsilyl-3,5-di-O-trifluoroacetyl-1-thio-α-D-arabinofuranoside 在 吡啶 、 四丁基氟化铵 、 溶剂黄146 作用下， 以 四氢呋喃 、 二氯甲烷 、 氯仿 、 异丙醇 、 Petroleum ether 为溶剂， 反应 27.67h， 生成 4-(2-chloroethoxy)phenyl 2-O-[3,5-di-O-benzoyl-β-D-arabinofuranosyl]-α-D-arabinofuranoside
  参考文献：
  名称：

  The use of O-trifluoroacetyl protection and profound influence of the nature of glycosyl acceptor in benzyl-free arabinofuranosylation

  摘要：

  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.

  DOI：

  10.1016/j.carres.2014.05.017
• 作为产物：
  描述：

  phenyl 3,5-di-O-benzoyl-1-thio-α-D-arabinofuranoside 在 2,4,6-三甲基吡啶 、 sodium methylate 、 sodium 2,2,2-trifluoroacetate 作用下， 以 甲醇 、 二氯甲烷 、 N,N-二甲基甲酰胺 为溶剂， 反应 52.0h， 生成 phenyl 2-O-triisopropylsilyl-3,5-di-O-trifluoroacetyl-1-thio-α-D-arabinofuranoside
  参考文献：
  名称：

  The use of O-trifluoroacetyl protection and profound influence of the nature of glycosyl acceptor in benzyl-free arabinofuranosylation

  摘要：

  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.

  DOI：

  10.1016/j.carres.2014.05.017

文献信息

• Bimodal concentration-dependent reactivity pattern of a glycosyl donor: Is the solution structure involved?
  作者：Leonid O. Kononov、Ksenia G. Fedina、Anna V. Orlova、Nikolay N. Kondakov、Polina I. Abronina、Nikita M. Podvalnyy、Alexander O. Chizhov

  DOI：10.1016/j.carres.2016.11.009

  日期：2017.1

  of the solution of 1, virtually do not depend on concentration suggesting formation of reacting species (supramers) of glycosyl donor with similar structures, hence reactivities, but considerably different from those formed in more dilute solutions. The found critical concentration (0.01 M) separates two concentration ranges of reaction solutions corresponding to two types of solution structure that

  阿拉伯呋喃糖基供体（1）的浓度（0.001-0.1 M）的变化已显示出可调节1活化发生的温度T（从-23摄氏度到+7摄氏度），反应时间（从1.5个小时开始）至3天）和形成的二糖的产率（从14％至82％）。在浓度超过0.01 M时，这些参数以及溶液1的比旋光度实际上并不取决于浓度，该浓度表明形成具有相似结构的糖基供体的反应物质（支持物），因此具有反应性，但与在更稀溶液中形成的那些。发现的临界浓度（0。01 M）分离了对应于两种类型溶液结构的两个浓度范围的反应溶液，这些溶液结构的特征是存在根本不同的糖基供体超分子，它们具有不同的化学性质。这些结果使人们重新审视了化合物的反应性和它们所参与的反应的选择性问题。