(Sp,Sc)-2-propyl 3-<<2-(trimethylsilyl)ethoxy>phosphinothioyl>-2-oxopropanoate | 137822-68-5

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (Sp,Sc)-2-propyl 3-<<2-(trimethylsilyl)ethoxy>phosphinothioyl>-2-oxopropanoate
• 英文别名: (S_p,S_c)-2-propyl 3-<<2-(trimethylsilyl)ethoxy>phosphinothioyl>-2-oxopropanoate；(S_p,S_c)-2-propyl 3-{[methyl(1-phenylethyl)amino][2-(trimethylsilyl)ethoxy]phosphinothioyl}-2-oxopropanoate
• CAS: 137822-68-5
• 化学式: C₂₀H₃₄NO₄PSSi
• 分子量: 443.62
• InChiKey: ZHILLJLXZSGDNU-QLXKLKPCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.86
• 重原子数：
  28.0
• 可旋转键数：
  11.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  55.84
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为反应物：
  描述：

  (Sp,Sc)-2-propyl 3-<<2-(trimethylsilyl)ethoxy>phosphinothioyl>-2-oxopropanoate 在 18-冠醚-6 、 cesium fluoride 作用下， 以 乙腈 为溶剂， 反应 30.0h， 以85%的产率得到(Sp,Sc)-2-propyl 3-<phosphinothioyl>-2-oxopropanoate
  参考文献：
  名称：

  Evidence for an intramolecular, stepwise reaction pathway for PEP phosphomutase catalyzed phosphorus-carbon bond formation

  摘要：

  The Tetrahymena pyriformis enzyme, phosphoenolpyruvate phosphomutase, catalyzes the rearrangement of phosphoenolpyruvate to the P-C bond containing metabolite, phosphonopyruvate. To distinguish between an intra- and intermolecular reaction pathway for this process an equimolar mixture of [P-O-18,C(2)-O-18]thiophosphonopyruvate and (all O-16) thiophosphonopyruvate was reacted with the phosphomutase, and the resulting products were analyzed by P-31 NMR. The absence of the cross-over product [C(2)-O-18]thiophosphonoenolpyruvate in the product mixture was interpreted as evidence for an intramolecular reaction pathway. To distinguish between a concerted and stepwise intramolecular reaction pathway the pure enantiomers of the chiral substrate [O-18]thiophosphonopyruvate were prepared and the stereochemical course of their conversion to chiral [O-18]thiophosphoenolpyruvate was determined. The assignments of the phosphorus configurations in the [O-18]thiophosphonopyruvate enantiomers reported earlier (McQueney, M. S.; Lee, S.-l.; Bowman, E.; Mariano, P. S.; Dunaway-Mariano, D. J. Am. Chem. Soc. 1989, 111, 6885-6887) were revised according to the finding that introduction of the O-18 label into the thiophosphonopyruvate precursor occurs with retention rather than with (the previously assumed) inversion of configuration. On the basis the observed conversion of (S(p))-[O-18]thiophosphonopyruvate to (S(p))-[O-18]thiophosphoenolpyruvate and (R(p))-[O-18]thiophosphonopyruvate to (Rp)-[O-18]thiophosphoenolpyruvate, it was concluded that the PEP phosphomutase reaction proceeds with retention of the phosphorus configuration and therefore by a stepwise mechanism. Lastly, the similar reactivity of the oxo- and thio-substituted phosphonopyruvate substrates (i.e., nearly equal V(max)) was interpreted to suggest that nucleophilic addition to the phosphorus atom is not rate limiting among the reaction steps.

  DOI：

  10.1021/jo00025a031
• 作为产物：
  描述：

  (s)-1-苯基乙基氨基甲酸乙酯 在 copper(l) iodide 、 lithium aluminium tetrahydride 、 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 19.0h， 生成 (Sp,Sc)-2-propyl 3-<<2-(trimethylsilyl)ethoxy>phosphinothioyl>-2-oxopropanoate
  参考文献：
  名称：

  Evidence for an intramolecular, stepwise reaction pathway for PEP phosphomutase catalyzed phosphorus-carbon bond formation

  摘要：

  The Tetrahymena pyriformis enzyme, phosphoenolpyruvate phosphomutase, catalyzes the rearrangement of phosphoenolpyruvate to the P-C bond containing metabolite, phosphonopyruvate. To distinguish between an intra- and intermolecular reaction pathway for this process an equimolar mixture of [P-O-18,C(2)-O-18]thiophosphonopyruvate and (all O-16) thiophosphonopyruvate was reacted with the phosphomutase, and the resulting products were analyzed by P-31 NMR. The absence of the cross-over product [C(2)-O-18]thiophosphonoenolpyruvate in the product mixture was interpreted as evidence for an intramolecular reaction pathway. To distinguish between a concerted and stepwise intramolecular reaction pathway the pure enantiomers of the chiral substrate [O-18]thiophosphonopyruvate were prepared and the stereochemical course of their conversion to chiral [O-18]thiophosphoenolpyruvate was determined. The assignments of the phosphorus configurations in the [O-18]thiophosphonopyruvate enantiomers reported earlier (McQueney, M. S.; Lee, S.-l.; Bowman, E.; Mariano, P. S.; Dunaway-Mariano, D. J. Am. Chem. Soc. 1989, 111, 6885-6887) were revised according to the finding that introduction of the O-18 label into the thiophosphonopyruvate precursor occurs with retention rather than with (the previously assumed) inversion of configuration. On the basis the observed conversion of (S(p))-[O-18]thiophosphonopyruvate to (S(p))-[O-18]thiophosphoenolpyruvate and (R(p))-[O-18]thiophosphonopyruvate to (Rp)-[O-18]thiophosphoenolpyruvate, it was concluded that the PEP phosphomutase reaction proceeds with retention of the phosphorus configuration and therefore by a stepwise mechanism. Lastly, the similar reactivity of the oxo- and thio-substituted phosphonopyruvate substrates (i.e., nearly equal V(max)) was interpreted to suggest that nucleophilic addition to the phosphorus atom is not rate limiting among the reaction steps.

  DOI：

  10.1021/jo00025a031