ethyl (E)-[2-13C]-3-cyclohexylpropenoate | 929704-74-5

• 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: ethyl (E)-[2-13C]-3-cyclohexylpropenoate
• CAS: 929704-74-5
• 化学式: C₁₁H₁₈O₂
• 分子量: 183.252
• InChiKey: SLGCKLRNFQEFEO-QLBIIAIVSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.69
• 重原子数：
  13.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.73
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  ethyl (E)-[2-13C]-3-cyclohexylpropenoate 在 4-二甲氨基吡啶 、 lithium hydroxide 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 12.0h， 生成 (E)-[2-13C]-S-2-acetamidoethyl 3-cyclohexylprop-2-enethioate
  参考文献：
  名称：

  Modular Polyketide Synthases and cis Double Bond Formation:  Establishment of Activated cis-3-Cyclohexylpropenoic Acid as the Diketide Intermediate in Phoslactomycin Biosynthesis

  摘要：

  The majority of modular polyketide synthase (PKS) systems which generate unsaturated products do so with trans double bonds. Phoslactomycin B (PLM B) presents a class of antitumor and antiviral natural polyketide products that have unique structural features, including a linear unsaturated backbone with one trans and three cis double bonds. There is substantial evidence that trans double bonds are established by ketoreductase-dehydratase (KR-DH) didomains within a PKS module. In cases where modules containing these didomains appear to generate product containing a cis double bond, there is no experimental evidence to determine if they do so directly or if they also form a trans double bond with a subsequent isomerization step. A critical step in addressing this issue is establishing the stereochemistry of the polyketide intermediate which passes to the subsequent module. Herein, we demonstrate through a series of experiments that an activated cis-3-cyclohexylpropenoic acid is the diketide intermediate which passes from module 1 to module 2 of the PLM PKS. The trans isomer of the diketide intermediate could not be processed directly into PLM B by module 2 but could be converted to PLM B by degradation to cyclohexanecarboxylic acid and elongation by the entire PLM PKS. These observations indicate not only that module 1 with a DH-KR didomain is responsible for establishing the C-14-C-15 cis double bond of PLM B but also that the subsequent modules of the PKS clearly discriminate between the cis- and trans-diketide intermediate and do not contain domains capable of catalyzing double bond isomerization.

  DOI：

  10.1021/ja068818t
• 作为产物：
  描述：

  膦酰基乙酸三乙酯-2-13C 、 环己烷基甲醛 在 18-冠醚-6 、 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 0.58h， 以75%的产率得到ethyl (Z)-[2-13C]-3-cyclohexylpropenoate
  参考文献：
  名称：

  Modular Polyketide Synthases and cis Double Bond Formation:  Establishment of Activated cis-3-Cyclohexylpropenoic Acid as the Diketide Intermediate in Phoslactomycin Biosynthesis

  摘要：

  The majority of modular polyketide synthase (PKS) systems which generate unsaturated products do so with trans double bonds. Phoslactomycin B (PLM B) presents a class of antitumor and antiviral natural polyketide products that have unique structural features, including a linear unsaturated backbone with one trans and three cis double bonds. There is substantial evidence that trans double bonds are established by ketoreductase-dehydratase (KR-DH) didomains within a PKS module. In cases where modules containing these didomains appear to generate product containing a cis double bond, there is no experimental evidence to determine if they do so directly or if they also form a trans double bond with a subsequent isomerization step. A critical step in addressing this issue is establishing the stereochemistry of the polyketide intermediate which passes to the subsequent module. Herein, we demonstrate through a series of experiments that an activated cis-3-cyclohexylpropenoic acid is the diketide intermediate which passes from module 1 to module 2 of the PLM PKS. The trans isomer of the diketide intermediate could not be processed directly into PLM B by module 2 but could be converted to PLM B by degradation to cyclohexanecarboxylic acid and elongation by the entire PLM PKS. These observations indicate not only that module 1 with a DH-KR didomain is responsible for establishing the C-14-C-15 cis double bond of PLM B but also that the subsequent modules of the PKS clearly discriminate between the cis- and trans-diketide intermediate and do not contain domains capable of catalyzing double bond isomerization.

  DOI：

  10.1021/ja068818t