Methanesulfonic acid (4aR,7S,8S,8aR)-8-(tert-butyl-dimethyl-silanyloxy)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl ester | 215441-79-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二恶烷
• 英文名称: Methanesulfonic acid (4aR,7S,8S,8aR)-8-(tert-butyl-dimethyl-silanyloxy)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl ester
• CAS: 215441-79-5
• 化学式: C₂₀H₃₂O₇SSi
• 分子量: 444.621
• InChiKey: OYLUWEXSVPVXPW-DZGDQSPQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.23
• 重原子数：
  29.0
• 可旋转键数：
  5.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  80.29
• 氢给体数：
  0.0
• 氢受体数：
  7.0

反应信息

• 作为反应物：
  描述：

  Methanesulfonic acid (4aR,7S,8S,8aR)-8-(tert-butyl-dimethyl-silanyloxy)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl ester 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 23.5h， 生成 Dithiocarbonic acid O-[(4aR,7S,8S,8aS)-8-(6-amino-purin-9-yl)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl] ester S-methyl ester
  参考文献：
  名称：

  Oligonucleotides Composed of 2‘-Deoxy-1‘,5‘-anhydro-d-mannitol Nucleosides with a Purine Base Moiety

  摘要：

  2'-Deoxy-D-mannitol nucleosides with a purine base moiety have been conveniently synthesized starting from 1,5-anhydro-4,6-O-benzylidene-D-glucito The 3-OH function of 1,5-anhydro-4,6-O-benzylidene-D-glucitol was selectively protected with tert-butyldimethylsilyl group, and the 2'-OH function was subsequently converted to the corresponding O-triflate derivative for the introduction of the nucleobase moieties. These nucleoside derivatives were transformed to 1,5-anhydro-4-O-(P-(2 -cyanoethyl)-P-(N,N-diisopropylamino)phosphinyl)-2-deoxy-6-O-monomethoxytrityl-3-O-(tert-butyldimethylsilyl)-D-mannitol with either a 2-(N(6)-benzoyladenin-9-yl) or a 2-(N(2)-isobutyrylguanin-9-yl) substituent as the building blocks for oligonucleotide synthesis. The corresponding fully modified oligonucleotides afford considerably less stable duplexes with RNA as compared to the 3-deoxy hexitol nucleic acid analogues described previously, The reason for the lower stability was investigated using molecular modeling, MD simulations of single strand MNA(GCGTAGCG) and MNA(GCGTAGCG) complexed with RNA(CGCAUCGC) in aqueous solution were performed by use of AMBER 4.1 with the particle mesh Ewald (PME) method for the treatment of long-range electrostatic interactions, Frequent hydrogen bonds between the 3'-hydroxyl and the 6'-O of the phosphate backbone of the following base changed the conformation of the single strand as well as the MNA:RNA complex. The MNA:RNA backbone widens up and shows partial unwinding and disruption of base pair hydrogen bonds consistent with their low hybridization potential.

  DOI：

  10.1021/jo9718511
• 作为产物：
  描述：

  甲基磺酰氯 、 (4aR,7S,8R,8aR)-8-[tert-butyl(dimethyl)silyl]oxy-2-phenyl-4,4a,6,7,8,8a-hexahydropyrano[3,2-d][1,3]dioxin-7-ol 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 2.0h， 以100%的产率得到Methanesulfonic acid (4aR,7S,8S,8aR)-8-(tert-butyl-dimethyl-silanyloxy)-2-phenyl-hexahydro-pyrano[3,2-d][1,3]dioxin-7-yl ester
  参考文献：
  名称：

  Oligonucleotides Composed of 2‘-Deoxy-1‘,5‘-anhydro-d-mannitol Nucleosides with a Purine Base Moiety

  摘要：

  2'-Deoxy-D-mannitol nucleosides with a purine base moiety have been conveniently synthesized starting from 1,5-anhydro-4,6-O-benzylidene-D-glucito The 3-OH function of 1,5-anhydro-4,6-O-benzylidene-D-glucitol was selectively protected with tert-butyldimethylsilyl group, and the 2'-OH function was subsequently converted to the corresponding O-triflate derivative for the introduction of the nucleobase moieties. These nucleoside derivatives were transformed to 1,5-anhydro-4-O-(P-(2 -cyanoethyl)-P-(N,N-diisopropylamino)phosphinyl)-2-deoxy-6-O-monomethoxytrityl-3-O-(tert-butyldimethylsilyl)-D-mannitol with either a 2-(N(6)-benzoyladenin-9-yl) or a 2-(N(2)-isobutyrylguanin-9-yl) substituent as the building blocks for oligonucleotide synthesis. The corresponding fully modified oligonucleotides afford considerably less stable duplexes with RNA as compared to the 3-deoxy hexitol nucleic acid analogues described previously, The reason for the lower stability was investigated using molecular modeling, MD simulations of single strand MNA(GCGTAGCG) and MNA(GCGTAGCG) complexed with RNA(CGCAUCGC) in aqueous solution were performed by use of AMBER 4.1 with the particle mesh Ewald (PME) method for the treatment of long-range electrostatic interactions, Frequent hydrogen bonds between the 3'-hydroxyl and the 6'-O of the phosphate backbone of the following base changed the conformation of the single strand as well as the MNA:RNA complex. The MNA:RNA backbone widens up and shows partial unwinding and disruption of base pair hydrogen bonds consistent with their low hybridization potential.

  DOI：

  10.1021/jo9718511

文献信息

• Synthesis of 1,5-Anhydro-D-Mannitol Nucleosides with a Purine Base Moeety
  作者：Nafizal Hossain、Piet Herdewijn

  DOI：10.1080/07328319808004713

  日期：1998.9

  D-Mannitol nucleosides with a purine base moiety have been conveniently synthesized strating from 1,5-anhydro-4,6-O-benzylidene-D-glucitol. The 3-OH function of 1,5-anhydro-4,6-O-benzylidene-D-glucitol was selectively protected with t-butyldimethylsilyl group and subsequently converted to the corresponding O-triflate derivative for the introduction of the nucleobase moietes. These nucleoside derivatives were transformed to 1,5-Anhydro-6-O-MMTr-2-(N(6)-benzoyladenin-9-yl)-2-deoxy-3-O-TBPMS-D-mannitol and 1,5-Anhydro-6-O-MMTr-2-(N(2)-isobutyrylguanin-9-yl)-2-deoxy-3-O-TBDMS-D-mannitol, useful as the building blocks for oligonucleotide synthesis. Also, the synthesis of the corresponding fully deprotected anhydrohexitol nucleosides were achieved for evaluation of antiviral activity test.