2-(trimethylsilyl)ethyl methylphosphonochloridothioate | 137792-50-8

• 分子结构分类: 有机化合物 - 有机磷化合物 - 有机硫代磷化合物
• 英文名称: 2-(trimethylsilyl)ethyl methylphosphonochloridothioate
• 英文别名: chloro-methyl-sulfanylidene-(2-trimethylsilylethoxy)-λ5-phosphane
• CAS: 137792-50-8
• 化学式: C₆H₁₆ClOPSSi
• 分子量: 230.771
• InChiKey: LOSWVYTXFPDNIB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  11.0
• 可旋转键数：
  4.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  2-(trimethylsilyl)ethyl methylphosphonochloridothioate 在 copper(l) iodide 、 正丁基锂 作用下， 以 四氢呋喃 、 乙醚 、 正己烷 为溶剂， 反应 12.0h， 生成 (Rp,Sc)-2-(trimethylsilyl)ethyl 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
• 作为产物：
  描述：

  2-(三甲硅基)乙醇 、 二氯甲基硫代膦 在 正丁基锂 作用下， 以 四氢呋喃 为溶剂， 反应 7.0h， 以49%的产率得到2-(trimethylsilyl)ethyl methylphosphonochloridothioate
  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