S-2-cyanoethyl thiophosphate mono tri-n-butylammonium salt | 135942-94-8

• 分子结构分类: 有机化合物 - 有机氮化合物
• 英文名称: S-2-cyanoethyl thiophosphate mono tri-n-butylammonium salt
• 英文别名: 2-cyanoethylsulfanylphosphonic acid;N,N-dibutylbutan-1-amine
• CAS: 135942-94-8
• 化学式: C₃H₆NO₃PS*C₁₂H₂₇N
• 分子量: 352.478
• InChiKey: MAFDKOCTNIDNKD-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.41
• 重原子数：
  22
• 可旋转键数：
  12
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  110
• 氢给体数：
  2
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  [(2R,3R,4R,5R)-4-acetyloxy-5-(2-amino-6-oxo-1H-purin-9-yl)-2-[(4-oxo-1,3,2-benzodioxaphosphinin-2-yl)oxymethyl]oxolan-3-yl] acetate 、 S-2-cyanoethyl thiophosphate mono tri-n-butylammonium salt 在 三正丁胺 、 sulfur 作用下， 生成
  参考文献：
  名称：

  Stereospecific synthesis of guanosine 5'-O-(1,2-dithiotriphosphates)

  摘要：

  The synthesis of the four diastereomers of guanosine 5'-O-(1,2-dithiotriphosphate) by two different approaches is described. 2',3'-Diacetylguanosine is phosphitylated with 2-chloro-4H-1,3,2-benzodioxaphosphorin-4-one to form 2, which upon reaction with S-2-cyanoethyl phosphorothioate and sulfur forms 3. Subsequent hydrolysis of this intermediate produces the two diastereomers of guanosine 5'-O-(1,2-dithiodiphosphate) (GDP-alpha-S-beta-S, 4). These can be phosphorylated by both acetate or pyruvate kinases. The R(p)R(p) as well as the S(p)R(p) diastereomers of guanosine 5'-O-(1,2-dithiotriphosphate) (GTP-alpha-S-beta-S, 5) can be obtained by reaction of (R(p))- or (S(p))-GDP-alpha-S-beta-S, respectively, with acetate kinase. Pyruvate kinase only accepts (S(p))-GDP-alpha-S-beta-S as substrate and therefore only (S(p)S(p))-GTP-alpha-S-beta-S is available by this route. All four diastereomers of GTP-alpha-S-beta-S can be synthesized by the second approach, in which 2 is reacted with thiopyrophosphate to produce a mixture of the diastereomers of GTP-alpha-S-beta-S and of guanosine 5'-O-(1,3-dithiotriphosphate) (GTP-alpha-S-gamma-S). The latter is removed by selective hydrolysis and subsequent chromatography. The four diastereomers of GTP-alpha-S-beta-S can be separated by HPLC according to their configuration at P-alpha into two groups consisting of the S(p)S(p)/S(p)R(p) and the R(p)S(p)/R(p)R(p) diastereomers. Glycerol kinase selectively hydrolyzes the diastereomers with the R(p) configuration at P-beta, thus making (S(p)S(p)- and (R(p)S(p)-GTP-alpha-S-beta-S available from the two groups. Myosin is stereospecific for reaction with diastereomers with the S(p) configuration at P-beta, allowing the isolation of the S(p)R(p) and R(p)R(p) diastereomers. P-31 NMR spectroscopy of the Cd2+ salts of the four diastereomers reveals two groups of complexes, which differ in their P-alpha-beta coupling constants which can be related to the arrangement of the guanosine and the gamma-phosphate as either cis or trans in the six-membered cyclic complex.

  DOI：

  10.1021/jo00020a029