(S)-nicotine Δ-^1',5'-iminium bisperchlorate | 71014-67-0

• 分子结构分类: 有机化合物 - 生物碱及其衍生物
• 英文名称: (S)-nicotine Δ-^1',5'-iminium bisperchlorate
• 英文别名: (S)-(-)-nicotine-Δ1'(5')-iminium diperchlorate
• CAS: 71014-67-0
• 化学式: C₁₀H₁₃N₂*ClHO₄*ClO₄
• 分子量: 361.136
• InChiKey: ZWPCGDJKEYYZGQ-XRIOVQLTSA-N

物化性质

• 熔点：
  228-232°C
• 溶解度：
  可溶于乙腈（少许）、水（少许）

计算性质

• 辛醇/水分配系数(LogP)：
  -6.18
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  194.39
• 氢给体数：
  1.0
• 氢受体数：
  8.0

反应信息

• 作为反应物：
  描述：

  (S)-nicotine Δ-^1',5'-iminium bisperchlorate 在 platinum(IV) oxide diclazuril 、 氘 作用下， 以 重水 为溶剂， 反应 3.5h， 以4.34 g的产率得到(S)-nicotine-5'(E)-d1
  参考文献：
  名称：

  Stereochemical studies on the cytochrome P-450 catalyzed oxidation of (S)-nicotine to the (S)-nicotine .DELTA.1'(5')-iminium species

  摘要：

  Mammals metabolize the tobacco alkaloid (S)-nicotine primarily to the lactam (S)-cotinine by a pathway involving an initial cytochrome P-450 catalyzed two-electron oxidation at the prochiral 5'-carbon atom. The stereochemical course of this oxidation was examined with human microsomal preparations and the E and Z diastereomers of (S)-nicotine-5'd1. The metabolically generated delta 1'(5')-iminium ion intermediate was trapped and analyzed as the corresponding diastereomeric 5'-cyano derivatives by a capillary column GC-EIMS selected ion monitoring assay. The results of these studies established that this biotransformation proceeds with the stereoselective abstraction of the 5'-pro-E proton, that is, the C-5' proton trans to the bulky pyridyl group. The observed stereoselectivity was independent of proton vs. deuteron abstraction. Additionally, the extent of (S)-cotinine formation was minor and did not influence the stereochemical composition of the metabolically derived alpha-cyano amines. Studies with male Dutch rabbit liver microsomal preparations gave similar results. These findings suggest that the structure of the complex formed between (S)-nicotine and the active site of cytochrome P-450 is highly ordered and dictates the stereochemical course of the reaction pathway.

  DOI：

  10.1021/jm00385a004
• 作为产物：
  描述：

  烟碱 在 高氯酸 作用下， 以 乙醇 为溶剂， 生成 (S)-nicotine Δ-^1',5'-iminium bisperchlorate
  参考文献：
  名称：

  Stereochemical studies on the cytochrome P-450 catalyzed oxidation of (S)-nicotine to the (S)-nicotine .DELTA.1'(5')-iminium species

  摘要：

  Mammals metabolize the tobacco alkaloid (S)-nicotine primarily to the lactam (S)-cotinine by a pathway involving an initial cytochrome P-450 catalyzed two-electron oxidation at the prochiral 5'-carbon atom. The stereochemical course of this oxidation was examined with human microsomal preparations and the E and Z diastereomers of (S)-nicotine-5'd1. The metabolically generated delta 1'(5')-iminium ion intermediate was trapped and analyzed as the corresponding diastereomeric 5'-cyano derivatives by a capillary column GC-EIMS selected ion monitoring assay. The results of these studies established that this biotransformation proceeds with the stereoselective abstraction of the 5'-pro-E proton, that is, the C-5' proton trans to the bulky pyridyl group. The observed stereoselectivity was independent of proton vs. deuteron abstraction. Additionally, the extent of (S)-cotinine formation was minor and did not influence the stereochemical composition of the metabolically derived alpha-cyano amines. Studies with male Dutch rabbit liver microsomal preparations gave similar results. These findings suggest that the structure of the complex formed between (S)-nicotine and the active site of cytochrome P-450 is highly ordered and dictates the stereochemical course of the reaction pathway.

  DOI：

  10.1021/jm00385a004

文献信息

• Stereochemical studies on the cytochrome P-450 catalyzed oxidation of (S)-nicotine to the (S)-nicotine .DELTA.1'(5')-iminium species
  作者：Lisa A. Peterson、Anthony Trevor、Neal Castagnoli

  DOI：10.1021/jm00385a004

  日期：1987.2

  Mammals metabolize the tobacco alkaloid (S)-nicotine primarily to the lactam (S)-cotinine by a pathway involving an initial cytochrome P-450 catalyzed two-electron oxidation at the prochiral 5'-carbon atom. The stereochemical course of this oxidation was examined with human microsomal preparations and the E and Z diastereomers of (S)-nicotine-5'd1. The metabolically generated delta 1'(5')-iminium ion intermediate was trapped and analyzed as the corresponding diastereomeric 5'-cyano derivatives by a capillary column GC-EIMS selected ion monitoring assay. The results of these studies established that this biotransformation proceeds with the stereoselective abstraction of the 5'-pro-E proton, that is, the C-5' proton trans to the bulky pyridyl group. The observed stereoselectivity was independent of proton vs. deuteron abstraction. Additionally, the extent of (S)-cotinine formation was minor and did not influence the stereochemical composition of the metabolically derived alpha-cyano amines. Studies with male Dutch rabbit liver microsomal preparations gave similar results. These findings suggest that the structure of the complex formed between (S)-nicotine and the active site of cytochrome P-450 is highly ordered and dictates the stereochemical course of the reaction pathway.