methyl (8S,10R,11R)-3,8,10,11-tetrahydroxy-3-oxo-2,4-dioxa-3lambda5-phosphaspiro[5.5]undecane-8-carboxylate | 159691-76-6

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: methyl (8S,10R,11R)-3,8,10,11-tetrahydroxy-3-oxo-2,4-dioxa-3lambda5-phosphaspiro[5.5]undecane-8-carboxylate
• 英文别名: methyl (8S,10R,11R)-3,8,10,11-tetrahydroxy-3-oxo-2,4-dioxa-3λ5-phosphaspiro[5.5]undecane-8-carboxylate
• CAS: 159691-76-6
• 化学式: C₁₀H₁₇O₉P
• 分子量: 312.213
• InChiKey: GVFDZUPKDCYJQZ-MATHAZKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -2.8
• 重原子数：
  20
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  143
• 氢给体数：
  4
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  methyl (8S,10R,11R)-3,8,10,11-tetrahydroxy-3-oxo-2,4-dioxa-3lambda5-phosphaspiro[5.5]undecane-8-carboxylate 在 sodium hydroxide 作用下， 反应 11.0h， 生成 <8(S)-(8α,10β,11α)>-8-Carboxy-3,8,10,11-tetrahydroxy-2,4-dioxa-3-phosphaspiro<5.5>undecane 3-oxide
  参考文献：
  名称：

  Synthesis and Evaluation of 3-Dehydroquinate Synthase Transition State Analogs

  摘要：

  Analogues have been synthesized of a six-membered, cyclic transition state likely involved in elimination of inorganic phosphate from an enzyme-bound, reactive intermediate formed during 3-dehydroquinate (DHQ) synthase catalysis. A spirocyclic carbaphosphodiester and ketocarbaphosphodiester analogue were both synthesized from quinic acid via a route where the essential spiro center was introduced by a ytterbium triflate-catalyzed aldol condensation. Spirocyclic carbaphosphodiester was a modest competitive inhibitor of DHQ synthase with an inhibition constant (K-i) of 6.7 x 10(-5) M. Enzyme-bound NADH formed during inhibition of enzyme by the spirocyclic carbaphosphodiester. Spirocyclic ketocarbaphosphodiester, even at concentrations of 0.5 mM, failed to inhibit DHQ synthase. These observations are discussed from the perspective of possible conformational constraints imposed by DHQ synthase on the reactive intermediate which undergoes elimination of inorganic phosphate relative to the ionization state of this reactive intermediate.

  DOI：

  10.1021/jo00104a013
• 作为产物：
  描述：

  Methyl <1(S)-(1α,3β,4α,5α)>-3-<(benzyloxymethyl)oxy>-1,4-bis<<(1,1-dimethylethyl)dimethylsilyl>oxy>-5-<<(triethylsilyl)oxy>ylidene>cyclohexane-1-carboxylate 在 palladium on activated charcoal 、 ytterbium(III) triflate 四氮唑 、 sodium tetrahydroborate 、 四丁基氟化铵 、 氢气 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 、 水 、 乙腈 为溶剂， 25.0 ℃ 、344.73 kPa 条件下， 反应 10.33h， 生成 methyl (8S,10R,11R)-3,8,10,11-tetrahydroxy-3-oxo-2,4-dioxa-3lambda5-phosphaspiro[5.5]undecane-8-carboxylate
  参考文献：
  名称：

  Synthesis and Evaluation of 3-Dehydroquinate Synthase Transition State Analogs

  摘要：

  Analogues have been synthesized of a six-membered, cyclic transition state likely involved in elimination of inorganic phosphate from an enzyme-bound, reactive intermediate formed during 3-dehydroquinate (DHQ) synthase catalysis. A spirocyclic carbaphosphodiester and ketocarbaphosphodiester analogue were both synthesized from quinic acid via a route where the essential spiro center was introduced by a ytterbium triflate-catalyzed aldol condensation. Spirocyclic carbaphosphodiester was a modest competitive inhibitor of DHQ synthase with an inhibition constant (K-i) of 6.7 x 10(-5) M. Enzyme-bound NADH formed during inhibition of enzyme by the spirocyclic carbaphosphodiester. Spirocyclic ketocarbaphosphodiester, even at concentrations of 0.5 mM, failed to inhibit DHQ synthase. These observations are discussed from the perspective of possible conformational constraints imposed by DHQ synthase on the reactive intermediate which undergoes elimination of inorganic phosphate relative to the ionization state of this reactive intermediate.

  DOI：

  10.1021/jo00104a013