N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-(3-oxa-1-thia-2-phosphaspiro[4.5]decan-2-yloxy)oxolan-2-yl]purin-6-yl]benzamide | 212574-97-5

• 分子结构分类: 有机化合物 - 苯类化合物 - 三苯基化合物
• 英文名称: N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-(3-oxa-1-thia-2-phosphaspiro[4.5]decan-2-yloxy)oxolan-2-yl]purin-6-yl]benzamide
• CAS: 212574-97-5
• 化学式: C₄₅H₄₆N₅O₇PS
• 分子量: 831.929
• InChiKey: AJVVPAMSUUIURL-CNGLVTPWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.1
• 重原子数：
  59
• 可旋转键数：
  13
• 环数：
  9.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  153
• 氢给体数：
  1
• 氢受体数：
  11

反应信息

• 作为反应物：
  描述：

  N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-(3-oxa-1-thia-2-phosphaspiro[4.5]decan-2-yloxy)oxolan-2-yl]purin-6-yl]benzamide 在 selenium 作用下， 以 苯 为溶剂， 反应 12.0h， 以59%的产率得到5'-O-(4,4'-dimethoxytrityl)-N⁶-benzoyl-deoxyadenosine-3'-O-(2-selena-spiro-4,4-pentamethylene-1,3,2-oxathiaphospholane)
  参考文献：
  名称：

  Oxathiaphospholane Approach to the Synthesis of Oligodeoxyribonucleotides Containing Stereodefined Internucleotide Phosphoroselenoate Function

  摘要：

  5'-O-DMT-deoxyribonucleoside-3'-O-(2-selena-4,4-pentamethylene-1,3,2-oxathiaphospholane) monomers, derivatives of dA, dC, dG, and T, can be resolved into pure P-diastereomers by silica gel column chromatography. They have been used for DBU-promoted, either solution- or solid-phase synthesis of P-stereodefined phosphoroselenoate analogues of oligodeoxyribonucleotides. Fast- and slow-eluting monomers are precursors of phosphoroselenoate internucleotide linkage of R-p and S-p absolute configuration, respectively.

  DOI：

  10.1021/ol051302e
• 作为产物：
  描述：

  1-mercapto-1,1-pentamethylenethan-2-ol 在 吡啶 、 N,N-二异丙基乙胺 、 三氯化磷 作用下， 以 乙腈 、 苯 为溶剂， 反应 0.58h， 生成 N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-(3-oxa-1-thia-2-phosphaspiro[4.5]decan-2-yloxy)oxolan-2-yl]purin-6-yl]benzamide
  参考文献：
  名称：

  Deoxyribonucleoside 3‘-O-(2-Thio- and 2-Oxo-“spiro”-4,4-pentamethylene-1,3,2-oxathiaphospholane)s:  Monomers for Stereocontrolled Synthesis of Oligo(deoxyribonucleoside phosphorothioate)s and Chimeric PS/PO Oligonucleotides

  摘要：

  New monomers, 5'-O-DMT-deoxyribonucleoside 3'-O-(2-thio-"spiro"-4,4-pentamethylene-1,3,2-oxathiaphospholane)s, were prepared and used for the stereocontrolled synthesis of PS-Oligos via the oxathiaphospholane approach. These monomers and their Zero analogues were used for the synthesis of "chimeric" constructs (PS/PO-Oligos) possessing phosphate and P-stereodefined phosphorothioate internucleotide linkages. The yield of a single coupling step is approximately 92-95%, and resulting oligomers are free of nucleobase- and sugar-phosphorothioate backbone modifications. Thermal dissociation studies showed that for heteroduplexes formed by [R-P]-, [S-P]-, or [mix]-PS/PO-T-10 with dA(12), dA(30), Or poly(dA), for each template, the melting temperatures, as well as free Gibbs' energies of dissociation process, are virtually equal. Stereochemical evidence derived from crystallographic analysis of one of the oxathiaphospholane monomers strongly supports the participation of pentacoordinate intermediates in the mechanism of the oxathiaphospholane ring-opening condensation.

  DOI：

  10.1021/ja973801j

文献信息

• Nucleoside 3′-<i>O</i>-(2-Oxo-“<i>Spiro</i>”-4.4-Pentamethylene-1.3.2-Oxathiaphospholane)S: Monomers For Stereocontrolled Synthesis Of Oligo(Nucleoside Phosphorothioate/Phosphate)S
  作者：Boleslaw Karwowski、Piotr Guga、Anna Kobylariska、Wojciech J. Stec

  DOI：10.1080/07328319808004710

  日期：1998.9

  Attempts at synthesis of "chimeric" oligonucleotide constructs (PO/PS-Oligos) possessing phosphate and P-stereodefined phosphorothioate internucleotide linkages via combined phosphoramidite/oxathiaphospholane methods were unsuccessful. Therefore, novel monomers for oxathiaphospholane method, namely 5'-O-DMT-deoxyribonucleoside 3'-O-(2-oxo-spiro-4.4-pentamethylene-1.3.2-oxathiaphospholane)s, were prepared and used together with their diastereomerically pure 2-thio analogues for the stereocontrolled synthesis off "chimeric" oligonucleotide constructs (PO/PS-Oligos).
• Selenium-Derivatized Oligonucleotides
  作者：Wojciech J. Stec、Anna Maciaszek、Piotr Guga

  DOI：10.1080/10426500801898242

  日期：2008.4.1

  Selenium-labelled macromolecules can be effectively analyzed by X-ray crystallography due to the phenomenon of multi-wavelength anomalous dispersion (MAD). The originally developed nucleoside 2-selena-1,3,2-oxathiaphospholane derivatives allow for synthesis of fully modified, stereodefined oligomers (up to approximately 15-mers) with any combination of internucleotide phosphoroselenoate linkages of RP or SP absolute configuration as well as unmodified phosphate bonds, which, in general, cannot be achieved using enzymatic methods.