methyl<1(R)-(1α,4α,5β)>-4-(benzoyloxy)-1-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-5-hydroxy-2-cyclohexene-1-carboxylate | 105539-80-8

• 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<1(R)-(1α,4α,5β)>-4-(benzoyloxy)-1-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-5-hydroxy-2-cyclohexene-1-carboxylate
• 英文别名: methyl(1(R)-(1α,4α,5β))-4-(benzoyloxy)-1-{[(1,1-dimethylethyl)dimethylsilyl]oxy}-5-hydroxy-2-cyclohexene-1-carboxylate
• CAS: 105539-80-8
• 化学式: C₂₁H₃₀O₆Si
• 分子量: 406.551
• InChiKey: QVAFWZLDWYXJCT-LZJOCLMNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.47
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.52
• 拓扑面积：
  82.06
• 氢给体数：
  1.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl<1(R)-(1α,4α,5β)>-4-(benzoyloxy)-1-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-5-hydroxy-2-cyclohexene-1-carboxylate 在 rhodium acethate 、 n,n-二甲基亚甲基碘化胺 、 三乙胺 、 碘甲烷 作用下， 以 苯 为溶剂， 反应 29.5h， 生成 methyl<1(R)-(1α,4α,5β)>-4-(benzoyloxy)-1-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-5-<<1-(methoxycarbonyl)ethenyl>oxy>-2-cyclohexene-1-carboxylate
  参考文献：
  名称：

  Synthesis of "iso-EPSP" and evaluation of its interaction with chorismate synthase

  摘要：

  DOI：

  10.1021/ja00285a031
• 作为产物：
  描述：

  (1S,3R,4R,5R)-3,4-O-Benzylidene-1,3,4-trihydroxy-6-oxabicyclo<3.2.1>octan-7-one 在 对甲苯磺酸 N-溴代丁二酰亚胺(NBS) 、 偶氮二异丁腈 、 diazabicycloundecane 作用下， 以 甲醇 、 乙腈 、 苯 为溶剂， 反应 23.0h， 生成 methyl<1(R)-(1α,4α,5β)>-4-(benzoyloxy)-1-<<(1,1-dimethylethyl)dimethylsilyl>oxy>-5-hydroxy-2-cyclohexene-1-carboxylate
  参考文献：
  名称：

  Synthesis of "iso-EPSP" and evaluation of its interaction with chorismate synthase

  摘要：

  DOI：

  10.1021/ja00285a031

文献信息

• Inversion of an Asymmetric Center in Carbocyclic Inhibitors of 3-Dehydroquinate Synthase: Examining and Exploiting the Mechanism for syn-Elimination during Substrate Turnover
  作者：Jean-Luc Montchamp、Jirong Peng、J. W. Frost

  DOI：10.1021/jo00102a025

  日期：1994.11

  Conversion of 3-deoxy-D-arabino-heptulosonic acid 7-phosphate (DAHP) into 3-dehydroquinate (DHQ) by the enzyme DHQ synthase has been proposed to proceed through a step where the phosphate monoester of a reactive intermediate mediates its own elimination. This hypothesis was tested by challenging DHQ synthase with a series of carbocyclic substrate analogues possessing an inverted methine carbon relative to the same asymmetric center in substrate DAHP which loses a proton during elimination of inorganic phosphate. Despite the stereochemical alteration, epicarbocyclic substrate analogues 5-[(phosphonooxy)methyl]-5-deoxyquinate, 5-(phosphonomethyl)-5-deoxyquinate, 5-(phosphonoethyl)-5-deoxyquinate, and 3-(phosphonooxy)quinate inhibited DHQ synthase with respective inhibition constants (K-i) of 30 nM, 55 nM, 30 mu M, and 53 mu M. These inhibitors were synthesized from quinic acid and with the exception of 3-(phosphono oxy)quinate, were assembled via a strategy employing intramolecular, radical cyclization to establish the stereocenter where the (phosphonooxy)methyl, phosphonomethyl, and phosphonoethyl moieties were attached to the carbocyclic ring. The observed diastereomeric promiscuity in the binding of epicarbocyclic substrate analogues by DHQ synthase is consistent with the hypothesized nonenzymic syn-elimination of inorganic phosphate during substrate turnover.