(S)-Methyl-phosphonothioic acid O-[(2R,3S,5R)-2-[bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester S-methyl ester | 129395-81-9

• 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: (S)-Methyl-phosphonothioic acid O-[(2R,3S,5R)-2-[bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester S-methyl ester
• 英文别名: 1-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[methyl(methylsulfanyl)phosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 129395-81-9
• 化学式: C₃₃H₃₇N₂O₈PS
• 分子量: 652.705
• InChiKey: ODYILYPFNAUQSK-KFEFBBAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4
• 重原子数：
  45
• 可旋转键数：
  12
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  138
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  (S)-Methyl-phosphonothioic acid O-[(2R,3S,5R)-2-[bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester S-methyl ester 在 二硫化碳 、 sodium hydride 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 lithium chloride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 生成 1-[(2R,4S,5R)-5-[[bis(4-methoxyphenyl)-phenylmethoxy]methyl]-4-[methyl-[[(2R,3S,5R)-5-(5-methyl-2,4-dioxopyrimidin-1-yl)-3-[methyl(methylsulfanyl)phosphoryl]oxyoxolan-2-yl]methoxy]phosphoryl]oxyoxolan-2-yl]-5-methylpyrimidine-2,4-dione
  参考文献：
  名称：

  Oligomeric Building Block Approach to the Synthesis of Diastereomerically Pure Pentathymidine 3‘,5‘-Methanephosphonates

  摘要：

  A method for a large-scale synthesis of stereodefined oligo(nucleoside 3',5'-methanephosphonates) has been developed, based on transient 3'-O protection, which allows for the conversion of the protecting chirally defined methanephosphonanilidate group, located at the 3' end of a stereoregular oligomer, into diastereomerically pure "oligomeric building blocks" for stereospecific coupling with the 5'-OH group of another oligonucleotide.

  DOI：

  10.1021/ol991376o
• 作为产物：
  描述：

  保护胸苷 在 吡啶 作用下， 反应 0.75h， 生成 (S)-Methyl-phosphonothioic acid O-[(2R,3S,5R)-2-[bis-(4-methoxy-phenyl)-phenyl-methoxymethyl]-5-(5-methyl-2,4-dioxo-3,4-dihydro-2H-pyrimidin-1-yl)-tetrahydro-furan-3-yl] ester S-methyl ester
  参考文献：
  名称：

  Base-Dependent Regioselective and P-Stereocontrolled Hydrolysis of Nucleoside 3‘-O-(O-2,4,6-Trimethylbenzoyl Methanephosphonothioate)s

  摘要：

  DOI：

  10.1021/jo981304v

文献信息

• Enantiodivergent Formation of C–P Bonds: Synthesis of P-Chiral Phosphines and Methylphosphonate Oligonucleotides
  作者：Dongmin Xu、Nazaret Rivas-Bascón、Natalia M. Padial、Kyle W. Knouse、Bin Zheng、Julien C. Vantourout、Michael A. Schmidt、Martin D. Eastgate、Phil S. Baran

  DOI：10.1021/jacs.9b13898

  日期：2020.3.25

  Phosphorous Incorporation (PI, abbreviated Π) reagents for the modular, scalable, and stereospecific synthesis of chiral phosphines and methyl-phosphonate nucleotides are reported. Synthesized from trans-limonene oxide, this reagent class displays an unexpected reactivity profile and enables access to chemical space distinct from that of the Phosphorous-Sulfur Incorporation reagents previously disclosed

  报告了用于手性膦和甲基膦酸核苷酸的模块化、可扩展和立体特异性合成的磷结合 (PI，缩写为 Π) 试剂。该试剂类由反式柠檬烯氧化物合成，显示出意想不到的反应性特征，并能够进入与之前公开的磷硫结合试剂不同的化学空间。在这里，适应性强的磷 (V) 支架能够连续添加碳亲核试剂以产生各种对映纯 CP 构建块。将三个碳亲核试剂添加到 Π，然后进行立体有择还原，得到有用的 P-手性膦；引入而不是单个甲基揭示了甲基膦酸酯寡核苷酸前体的首次立体定向合成。虽然两种 Π 对映异构体都可用，
• Stereochemistry of the DBU/LiCl-Assisted Nucleophilic Substitution at Phosphorus in Nucleoside-3‘-<i>O</i>-(<i>Se</i>-methyl Methanephosphonoselenolate)s
  作者：Lucyna A. Woźniak、Michał Wieczorek、Jarosław Pyzowski、Wiesław Majzner、Wojciech J. Stec

  DOI：10.1021/jo980225g

  日期：1998.8.1

  The crystal and molecular structure of diastereomerically pure N-4-benzoyl-2'-deoxycytidine 3'-O-(Se-methyl methanephosphonoselenolate (FAST-eluted) (4, R = H, B = C-Bz) and 5'-O-pixylthymidine 3'-O-(S-methyl methanephosphonothiolate (FAST-eluted) (5) have been elucidated by X-ray crystallography. The absolute configuration at the phosphorus atom in both compounds is Sp. Each FAST-4' (R = DMT, B = C-Bz) and FAST-5 (R = Px, B = Thy) in the process of DBU/LiCl-assisted condensation with 3'-O-acetyl-N-4-benzoylcytidine and 3'-O-acetylthymidine gave after deprotection (S-P)-dicytidine-(3',5')-methanephosphonate and (S-P)-dithymidine-(3',5')-methanephosphonate, respectively. Unambiguous assignment of the absolute configuration at the phosphorus in 4 (R = H, B = C-Bz) and 5 (R = Pr, B = Thy) allows for stereochemical correlation and the conclusion that DBU/LiCl-assisted nucleophilic substitution at phosphorus occurs with net inversion of configuration, in contrast to our earlier erroneous deduction,(5) Moreover, the knowledge of the absolute configuration at the phosphorus atom in both 4 (R = H, B = C-Bz) and 5 (R = Px, B = Thy) allows for assignment of the absolute configuration at phosphorus in precursors of 4' and 5, such as 5'-O-DMT-nucleoside 3'-O-methanephosphonothioanilidates (6), methanephosphonoanilidates (8), and methanephosphonoselenoanilidates (9).
• Base-Dependent Regioselective and P-Stereocontrolled Hydrolysis of Nucleoside 3‘-<i>O</i>-(<i>O</i>-2,4,6-Trimethylbenzoyl Methanephosphonothioate)s
  作者：Lucyna A.Woźniak,、Arkadiusz Chworoś、Jarosław Pyzowski、Wojciech J. Stec

  DOI：10.1021/jo981304v

  日期：1998.11.1
• Oligomeric Building Block Approach to the Synthesis of Diastereomerically Pure Pentathymidine 3‘,5‘-Methanephosphonates
  作者：Jaroslaw Pyzowski、Lucyna A. Wozniak、Wojciech J. Stec

  DOI：10.1021/ol991376o

  日期：2000.3.1

  A method for a large-scale synthesis of stereodefined oligo(nucleoside 3',5'-methanephosphonates) has been developed, based on transient 3'-O protection, which allows for the conversion of the protecting chirally defined methanephosphonanilidate group, located at the 3' end of a stereoregular oligomer, into diastereomerically pure "oligomeric building blocks" for stereospecific coupling with the 5'-OH group of another oligonucleotide.