(2R,3R,4S,5S)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-5-(2,4,6-trifluorophenyl)oxolane | 631899-57-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3R,4S,5S)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-5-(2,4,6-trifluorophenyl)oxolane
• CAS: 631899-57-5
• 化学式: C₃₂H₂₉F₃O₄
• 分子量: 534.575
• InChiKey: ASLFMICWLQJIAK-RRPOSWPMSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.93
• 重原子数：
  39.0
• 可旋转键数：
  11.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  36.92
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  (2R,3R,4S,5S)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-5-(2,4,6-trifluorophenyl)oxolane 在 吡啶 、 N-甲基咪唑 、 甲酸 、 palladium 10% on activated carbon 、 氢气 、 silver nitrate 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 、 甲醇 、 乙酸乙酯 为溶剂， 20.0 ℃ 、101.33 kPa 条件下， 反应 16.5h， 生成 2-O-[(tert-butyl)-dimethylsilyl]-1-deoxy-5-O-(4,4'-dimethoxytrityl)-3-(2-cyanoethyl-N,N-diisopropylphosphoramidite)-1-(2,4,6-trifluorophenyl)-β-D-ribofuranose
  参考文献：
  名称：

  通过氟在碱基类似物中的位置控制蛋白质-RNA 复合物的稳定性

  摘要：

  描述了在参与 SL2 RNA 和 U1A 蛋白之间叠加相互作用的位置处取代的非极性碱基类似物的电子特性的修改效果。观察到与仅在单个氟原子的取代位置不同的碱基类似物形成的复合物之间的稳定性存在惊人的大差异。非极性碱基类似物和氨基酸侧链之间相互作用的高级从头计算的结果与实验观察到的复杂稳定性趋势相关，这表明由于氟的位置和程度的变化导致堆积相互作用的变化取代有助于氟取代对 U1A-SL2 RNA 复合物稳定性的影响。

  DOI：

  10.1021/ja102601h
• 作为产物：
  描述：

  2,3,5-三苄氧基-D-核糖酸-1,4-内酯 在 三乙基硅烷 、 正丁基锂 、 三氟化硼乙醚 作用下， 以 乙醚 、 正己烷 、 二氯甲烷 为溶剂， 反应 5.33h， 生成 (2R,3R,4S,5S)-3,4-bis(phenylmethoxy)-2-(phenylmethoxymethyl)-5-(2,4,6-trifluorophenyl)oxolane
  参考文献：
  名称：

  通过氟在碱基类似物中的位置控制蛋白质-RNA 复合物的稳定性

  摘要：

  描述了在参与 SL2 RNA 和 U1A 蛋白之间叠加相互作用的位置处取代的非极性碱基类似物的电子特性的修改效果。观察到与仅在单个氟原子的取代位置不同的碱基类似物形成的复合物之间的稳定性存在惊人的大差异。非极性碱基类似物和氨基酸侧链之间相互作用的高级从头计算的结果与实验观察到的复杂稳定性趋势相关，这表明由于氟的位置和程度的变化导致堆积相互作用的变化取代有助于氟取代对 U1A-SL2 RNA 复合物稳定性的影响。

  DOI：

  10.1021/ja102601h

文献信息

• Synthesis of Modified RNA-Oligonucleotides for Structural Investigations
  作者：A. [Zbreve]ivković、J. W. Engels

  DOI：10.1081/ncn-120022827

  日期：2003.10

  incorporated and tested in a defined A, U- rich RNA sequence (12-mer, 5′-CUU UUC XUU CUU-3′ paired with 3′-GAA AAG YAA GAA-5’) (Schweitzer, B.A.; Kool, E.T. Aromatic nonpolar nucleosides as hydrophobic isosters of pyrimidine and purine nucleosides. J. Org. Chem. 1994, 59, 7238 pp.). Only one position was modified, marked as X and Y respectively. UV melting profiles of those oligonucleotides were measured

  摘要RNA具有比DNA更高的结构多样性，是生命生物学中的重要分子。它显示了许多二级结构，例如双链体，发夹环，凸起，内部环等。但是，在天然RNA中，碱基仅限于四个主要结构U，C，A和G，因此可以用于研究碱基堆积，碱基配对和氢键的参数是有限的。我们合成了不同的RNA修饰基团氟修饰：1'-deoxy-1'-（2,4,6-trifluorophenyl）-ß-D-ribfuranose（F），1'-deoxy-1'-（2,4,5 -三氟苯基）-β-D-呋喃核糖（M）和1'-脱氧-1'-（5-三氟甲基-1H-苯并咪唑-1-基）-β-D-核呋喃糖（D）。那些亚酰胺掺入并在确定的富含U，U的RNA序列（12-mer，5'-CUU UUC XUU CUU-3'与3'-GAA AAG YAA GAA-5'配对（Schweitzer，BA; Kool，ET）芳香非极性核苷作为嘧啶和嘌呤核苷的疏水等位异构体。J
• Three different fluoro- or chloro-substituted 1′-deoxy-1′-phenyl-β-<scp>D</scp>-ribofuranoses
  作者：Jan W. Bats、Aleksandra Živković、Jörg Parsch、Joachim W. Engels

  DOI：10.1107/s2053229614004999

  日期：2014.4.15

  Crystal structures are reported for three fluoro- or chloro-substituted 1′-deoxy-1′-phenyl-β-D-ribofuranoses, namely 1′-deoxy-1′-(2,4,5-trifluorophenyl)-β-D-ribofuranose, C₁₁H₁₁F₃O₄, (I), 1′-deoxy-1′-(2,4,6-trifluorophenyl)-β-D-ribofuranose, C₁₁H₁₁F₃O₄, (II), and 1′-(4-chlorophenyl)-1′-deoxy-β-D-ribofuranose, C₁₁H₁₃ClO₄, (III). The five-membered furanose ring of the three compounds has a conformation between a C2′-endo,C3′-exotwist and a C2′-endoenvelope. The ribofuranose groups of (I) and (III) are connected by intermolecular O—H...O hydrogen bonds to six symmetry-related molecules to form double layers, while the ribofuranose group of (II) is connected by O—H...O hydrogen bonds to four symmetry-related molecules to form single layers. The O...O contact distance of the O—H...O hydrogen bonds ranges from 2.7172 (15) to 2.8895 (19) Å. Neighbouring double layers of (I) are connected by a very weak intermolecular C—F...π contact. The layers of (II) are connected by one C—H...O and two C—H...F contacts, while the double layers of (III) are connected by a C—H...Cl contact. The conformations of the molecules are compared with those of seven related molecules. The orientation of the benzene ring is coplanar with the H—C1′ bond or bisecting the H—C1′—C2′ angle, or intermediate between these positions. The orientation of the benzene ring is independent of the substitution pattern of the ring and depends mainly on crystal-packing effects.

  报告了三种氟或氯取代的 1′-脱氧-1′-苯基-β-D-呋喃核糖的晶体结构，即 1′-脱氧-1′-(2,4,5-三氟苯基)-β-D-呋喃核糖、C11H11F3O4，(I)；1′-脱氧-1′-(2,4,6-三氟苯基)-β-D-呋喃核糖， ，(II)；以及 1′-(4-氯苯基)-1′-脱氧-β-D-呋喃核糖，C11H13ClO4，(III)。这三种化合物的五元呋喃糖环的构象介于 C2′-内旋、C3′-外旋和 C2′-内包络之间。(I)和(III)的核呋喃糖基团通过分子间 O-H...O 氢键与六个对称相关分子连接形成双层，而(II)的核呋喃糖基团通过 O-H...O 氢键与四个对称相关分子连接形成单层。O-H...O 氢键的 O...O 接触距离从 2.7172 (15) Å 到 2.8895 (19) Å 不等。(I)的相邻双层通过非常微弱的分子间 C-F...π 接触连接。(II)的双层通过一个 C-H...O和两个 C-H...F接触连接，而(III)的双层则通过一个 C-H...Cl接触连接。这些分子的构象与七个相关分子的构象进行了比较。苯环的取向与 H-C1′ 键共面，或与 H-C1′-C2′ 角成二叉，或介于这两个位置之间。苯环的取向与苯环的取代模式无关，主要取决于晶体的堆积效应。
• RNA RECOGNITION BY FLUOR-AROMATIC SUBSTITUTED
  作者：A. Zivković、J. W. Engels

  DOI：10.1081/ncn-200059755

  日期：2005.4.1

  RNA exhibits a higher structural diversity than DNA and is an important molecule in the biology of life. It shows a number of secondary structures such as duplexes, hairpin loops, bulges, internal loops, etc. However, in natural RNA, bases are limited to the four Predominant structures Q, C, A, and G and so the number of compounds that can be used for investigation of parameters of base stacking, base pairing, and hydrogen bond is limited. We synthesized different fluoromodifications of RNA building blocks: 1'-deoxy- 1'-phenyl-beta-D-ribofuranose (B), 1'-deoxy- 1'-(4-fluorophenyl)-beta-D-ribofuranose (4 FB), 1'-deoxy- 1'-(2,4-difluorophenyl)-beta-D-ribofuranose (2,4 DFB), 1'-deoxy-1'-(2,4,5-trifluorophenyl)-beta-D-ribofuranose (2,4,5 TFB), 1'-deoxy-1'-(2,4,6-trifluorophenyl)-beta-D-ribofuranose, 1'-deoxy- 1'-(pentafluorophenyl)-beta-D-ribofuranose (PFB), 1'-deoxy-1'-(benzimidazol-1-yl)-beta-D-ribofuranose (BI), 1'-deoxy-1'-(4-fluoro- 1H-benzimidazol-1-yl)-beta-D-ribofuranose (4 FBI), 1'-deoxy-1'-(6-fluoro-1H-benzimidazol-1-y1)-beta-D-ribofuranose(6FBI), 1'-deoxy-1'-(4,6-difluoro-IH-benzimidazol-1-yl)-beta-D-ribofuranose(4,6 DFBI), 1'-deoxy-1'-(4-trifluoromethyl-1H-benzimidazol-1-yl)-beta-D-ribofuranose (4 TFM), 1'-deoxy-1'-(5-trifluoromethyl-1H-benzimidazol-1-yl)-beta-D-ribofuranose (5 TFM), and 1'-deoxy-1'-(6-trifluoromethyl- 1H-benzimidazol-1-yl)-beta-D-ribofuranose (6 TFM). These amidites were incorporated and tested in a defined A, U-rich RNA sequence (12-mer, 5'-CUU UUC XUU CUU-3' paired with 3'-GAA AAG YAA GAA-5'). Ono one position was modified, marked as X and Y, respectively. UV melting profiles of those oligonucleotides were measured.