5’-O-DMT-N⁶-benzoyl-2’-deoxyadenosine-3’-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane) | 865716-19-4

• 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: 5’-O-DMT-N⁶-benzoyl-2’-deoxyadenosine-3’-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)
• 英文别名: N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[(2-sulfanylidene-3-oxa-1-thia-2lambda5-phosphaspiro[4.5]decan-2-yl)oxy]oxolan-2-yl]purin-6-yl]benzamide；N-[9-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[(2-sulfanylidene-3-oxa-1-thia-2λ5-phosphaspiro[4.5]decan-2-yl)oxy]oxolan-2-yl]purin-6-yl]benzamide
• CAS: 865716-19-4
• 化学式: C₄₅H₄₆N₅O₇PS₂
• 分子量: 863.995
• InChiKey: OJAKDFWWPJIQLY-CNGLVTPWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.3
• 重原子数：
  60
• 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：
  186
• 氢给体数：
  1
• 氢受体数：
  12

反应信息

• 作为反应物：
  描述：

  5’-O-DMT-N⁶-benzoyl-2’-deoxyadenosine-3’-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane) 在 磷酸 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 5.0h， 生成 5’-O-DMT-N⁶-benzoyl-2’-deoxyadenosine-3’-O-(α-thiodiphosphate)
  参考文献：
  名称：

  2-烷氧基-2-硫代-1,3,2-氧代磷酰胺与焦磷酸根阴离子开环反应中立体选择性的意外损失

  摘要：

  DBU与焦磷酸根或亚甲基二膦酸酯阴离子的反应促进了核苷3'- O-和核苷5'- O-（2-硫代-4,4-戊亚甲基-1,3,2-氧杂磷酰膦）单体中的开环进行而立体选择性的损失很大。迄今为止，根据磷原子的绝对构型，广泛接受的缩合立体保持机理与一种立体转化机理有关，最有可能在不带电荷的中间体中进行分子内配体-配体交换。手性27：155–122，2015。©2014 Wiley Periodicals，Inc

  DOI：

  10.1002/chir.22398
• 作为产物：
  描述：

  N6-苯甲酰基-5'-O-(4,4'-二甲氧基三苯基)-2'-脱氧腺苷 在 sulfur 、 N,N-二异丙基乙胺 作用下， 以 乙腈 为溶剂， 反应 12.08h， 生成 5’-O-DMT-N⁶-benzoyl-2’-deoxyadenosine-3’-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)
  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

• Oxathiaphospholane Approach to the Synthesis of Oligodeoxyribonucleotides Containing Stereodefined Internucleotide Phosphoroselenoate Function
  作者：Piotr Guga、Anna Maciaszek、Wojciech J. Stec

  DOI：10.1021/ol051302e

  日期：2005.9.1

  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.
• Deoxyribonucleoside 3‘-<i>O</i>-(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
  作者：Wojciech J. Stec、Bolesław Karwowski、Małgorzata Boczkowska、Piotr Guga、Maria Koziołkiewicz、Marek Sochacki、Michał W. Wieczorek、Jarosław Błaszczyk

  DOI：10.1021/ja973801j

  日期：1998.7.1

  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.
• Unexpected Loss of Stereoselectivity in Ring-Opening Reaction of 2-Alkoxy-2-Thio-1,3,2-Oxathiaphospholanes With a Pyrophosphate Anion
  作者：Piotr Guga、Agnieszka Tomaszewska

  DOI：10.1002/chir.22398

  日期：2015.2

  A reaction of DBU promoted ring opening in nucleoside‐3'‐O‐ and nucleoside‐5'‐O‐(2‐thio‐4,4‐pentamethylene‐1,3,2‐oxathiaphospholane) monomers with a pyrophosphate or a methylenediphosphonate anion proceeds with substantial loss of stereoselectivity. Depending on the absolute configuration of the phosphorus atom, so far widely accepted the stereoretentive mechanism of condensation is accompanied by

  DBU与焦磷酸根或亚甲基二膦酸酯阴离子的反应促进了核苷3'- O-和核苷5'- O-（2-硫代-4,4-戊亚甲基-1,3,2-氧杂磷酰膦）单体中的开环进行而立体选择性的损失很大。迄今为止，根据磷原子的绝对构型，广泛接受的缩合立体保持机理与一种立体转化机理有关，最有可能在不带电荷的中间体中进行分子内配体-配体交换。手性27：155–122，2015。©2014 Wiley Periodicals，Inc