1,4-anhydro-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-erythro-pent-1-entiol | 1160370-59-1

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二氢呋喃
• 英文名称: 1,4-anhydro-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-erythro-pent-1-entiol
• 英文别名: 1,4-anhydro-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-erythro-pent-1-enitol；(6aR,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,9a-dihydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocine
• CAS: 1160370-59-1
• 化学式: C₁₇H₃₄O₄Si₂
• 分子量: 358.626
• InChiKey: VWOBHQFCAOMLOS-DLBZAZTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.86
• 重原子数：
  23
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  36.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1,4-anhydro-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-erythro-pent-1-entiol 在 2,4,6-tri-tertiary-butylpyridinium hydrochloride salt 、 水 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以45.946%的产率得到
  参考文献：
  名称：

  CH···阴离子相互作用通过立体受阻的2,4,6-三叔丁基吡啶鎓盐酸盐辅助将水加到乙二醇中。

  摘要：

  在温和的条件下，庞大的碱式2,4,6-三叔丁基吡啶的共轭酸可催化在不同的水浓度下由糖基合成甲硅烷基保护的2-脱氧半缩醛及其二聚产物。反应结果中水浓度的临界值表明了大体积吡啶盐的独特机理，而不是通过一般的布朗斯台德酸机理。如此合成的各种甲硅烷基保护的半缩醛已成功用于α和β糖苷的立体选择性合成。

  DOI：

  10.1021/acs.orglett.0c00348
• 作为产物：
  描述：

  phenyl 3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-2-deoxy-1-thio-D-erythro-pentofuranose S-oxide 在 N,N-二异丙基乙胺 作用下， 以 5,5-dimethyl-1,3-cyclohexadiene 为溶剂， 反应 1.0h， 以84%的产率得到1,4-anhydro-2-deoxy-3,5-O-(1,1,3,3-tetraisopropyldisiloxane-1,3-diyl)-D-erythro-pent-1-entiol
  参考文献：
  名称：

  Electrophilic glycosidation employing 3,5-O-(di-tert-butylsilylene)-erythro-furanoid glycal leads to exclusive formation of the β-anomer: synthesis of 2′-deoxynucleosides and its 1′-branched analogues

  摘要：

  Stereoselectivity in N-iodosuccimide (NIS)-mediated electrophilic glycosidation was examined by employing 2,4-bis-O-(trimethylsilyl)thymine and three different silyl-protected erythro-furanoid glycals 12, 16, and 18. As a result, it was found that 3,5-O-(di-t-butylsilylene)-protected 18 gave only the beta-anomer (21). The remarkable stereoselectivity observed by employing 18 is discussed on the basis of its X-ray crystallographic analysis. 1-Substituted glycals gave the corresponding beta-anomer, again exclusively, to provide access to 1'-branched 2'-deoxynucleosides. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2010.04.043

文献信息

• Organocatalytic Conversion of Nucleosides to Furanoid Glycals
  作者：Edna Mao、Cheol K. Chung、Yining Ji、Yu-hong Lam、Peter E. Maligres

  DOI：10.1021/acs.joc.1c00555

  日期：2021.6.4

  2′-deoxynucleosides to furanoid glycals have been discovered. These phosphorimides, (Ph2PS)2NH and (Ph2PSe)2NH, were shown to effectively mediate persilylation of 2′-deoxynucleosides allowing the elimination of the nucleobase giving the corresponding glycal. These mild conditions were demonstrated in the syntheses of glycals with various substitution patterns while minimizing the formation of undesired byproducts

  已经发现了一类对将 2'-脱氧核苷转化为呋喃糖苷具有高活性的有机催化剂。这些磷酰亚胺(Ph 2 PS) 2 NH 和 (Ph 2 PSe) 2 NH 显示出可有效介导 2'-脱氧核苷的全甲硅烷基化，从而消除核碱基，产生相应的糖基。这些温和的条件在具有各种取代模式的糖醛的合成中得到了证明，同时最大限度地减少了不需要的副产物的形成并扩大了该方法的范围。
• Hydrogen-bond self-assembly of DNA-base analogues — Experimental results
  作者：Felaniaina Rakotondradany、Hanadi Sleiman、M. A. Whitehead

  DOI：10.1139/v09-028

  日期：2009.5

  A novel biomimetic DNA analogue with fluorescence has been synthesized to generate functional supramolecular architectures. Experimental studies show that triaminopyrimidine nucleoside (2) undergoes a sterically controlled self-assembly into hydrogen-bonded linear tapes and hexameric rosettes. Self-association of the hydrogen-bonded triaminopyrimidine–cyanuric acid complex into elongated, rodlike nanostructures was shown by dynamic light scattering and transmission electron microscopy, suggesting hierarchical formation of higher-order, π-stacked assemblies. The hydrogen-bond self-assembly of the DNA analogue decreased the fluorescence of the nucleosides. This guest-induced fluorescence quenching can be used to develop DNA-hybridization probes. MM⁺ molecular modelling and semi-empirical molecular orbital PM3 calculations (1) predicted the incorporation of triaminopyrimidine nucleoside into new types of artificial DNA strands and triplex formation with natural, complementary DNA strands containing thymine (1).

  我们合成了一种具有荧光功能的新型仿生物 DNA 类似物，以生成功能性超分子结构。实验研究表明，三氨基嘧啶核苷（2）通过立体控制自组装成氢键线性带和六聚体花环。动态光散射和透射电子显微镜显示，氢键三氨基嘧啶-氰尿酸复合物自组装成拉长的棒状纳米结构，表明高阶π堆叠组装体的分层形成。DNA 类似物的氢键自组装降低了核苷的荧光。这种客体诱导的荧光淬灭可用于开发 DNA 杂交探针。MM+ 分子建模和半经验分子轨道 PM3 计算（1）预测了三氨基嘧啶核苷与新型人工 DNA 链的结合，以及与含有胸腺嘧啶的天然互补 DNA 链形成三重体（1）。
• C–H···Anion Interactions Assisted Addition of Water to Glycals by Sterically Hindered 2,4,6-Tri-<i>tert</i>-butylpyridinium Hydrochloride
  作者：Ananya Mukherji、Pavan K. Kancharla

  DOI：10.1021/acs.orglett.0c00348

  日期：2020.3.20

  conjugate acid of the bulky base 2,4,6-tri-tert-butylpyridine, under mild conditions, catalyzes the synthesis of silyl-protected 2-deoxy-hemiacetals and their dimerized products from glycals at varying concentrations of water. The criticality of the concentration of water in the reaction outcome is indicative of a unique mechanistic pathway for the bulky pyridine salt and not via the general Brønsted acid

  在温和的条件下，庞大的碱式2,4,6-三叔丁基吡啶的共轭酸可催化在不同的水浓度下由糖基合成甲硅烷基保护的2-脱氧半缩醛及其二聚产物。反应结果中水浓度的临界值表明了大体积吡啶盐的独特机理，而不是通过一般的布朗斯台德酸机理。如此合成的各种甲硅烷基保护的半缩醛已成功用于α和β糖苷的立体选择性合成。
• Electrophilic glycosidation employing 3,5-O-(di-tert-butylsilylene)-erythro-furanoid glycal leads to exclusive formation of the β-anomer: synthesis of 2′-deoxynucleosides and its 1′-branched analogues
  作者：Kazuhiro Haraguchi、Kiju Konno、Kaori Yamada、Yasuyuki Kitagawa、Kazuo T. Nakamura、Hiromichi Tanaka

  DOI：10.1016/j.tet.2010.04.043

  日期：2010.6

  Stereoselectivity in N-iodosuccimide (NIS)-mediated electrophilic glycosidation was examined by employing 2,4-bis-O-(trimethylsilyl)thymine and three different silyl-protected erythro-furanoid glycals 12, 16, and 18. As a result, it was found that 3,5-O-(di-t-butylsilylene)-protected 18 gave only the beta-anomer (21). The remarkable stereoselectivity observed by employing 18 is discussed on the basis of its X-ray crystallographic analysis. 1-Substituted glycals gave the corresponding beta-anomer, again exclusively, to provide access to 1'-branched 2'-deoxynucleosides. (C) 2010 Elsevier Ltd. All rights reserved.