methyl (1S,3R,4R,5R)-1,4-bis[[tert-butyl(dimethyl)silyl]oxy]-3-formyl-3-(hydroxymethyl)-5-(phenylmethoxymethoxy)cyclohexane-1-carboxylate | 1055038-65-7

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: methyl (1S,3R,4R,5R)-1,4-bis[[tert-butyl(dimethyl)silyl]oxy]-3-formyl-3-(hydroxymethyl)-5-(phenylmethoxymethoxy)cyclohexane-1-carboxylate
• CAS: 1055038-65-7
• 化学式: C₃₀H₅₂O₈Si₂
• 分子量: 596.909
• InChiKey: JXDFLRHNQWGUMR-LPKQAODOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.84
• 重原子数：
  40
• 可旋转键数：
  15
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  101
• 氢给体数：
  1
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  methyl (1S,3R,4R,5R)-1,4-bis[[tert-butyl(dimethyl)silyl]oxy]-3-formyl-3-(hydroxymethyl)-5-(phenylmethoxymethoxy)cyclohexane-1-carboxylate 在 四氮唑 、 sodium tetrahydroborate 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 6.0h， 生成 methyl (8S,10R,11R)-8,11-bis[[tert-butyl(dimethyl)silyl]oxy]-3-phenylmethoxy-10-(phenylmethoxymethoxy)-2,4-dioxa-3-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
• 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-(hydroxymethyl)cyclohexane-1-carboxylate 在 ytterbium(III) triflate 草酰氯 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 水 、 苯 为溶剂， 反应 5.25h， 生成 methyl (1S,3R,4R,5R)-1,4-bis[[tert-butyl(dimethyl)silyl]oxy]-3-formyl-3-(hydroxymethyl)-5-(phenylmethoxymethoxy)cyclohexane-1-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