didemethylpetrosin D | 211759-06-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 喹嗪类
• 英文名称: didemethylpetrosin D
• 英文别名: (1R,7R,15S,21S,29S,30R)-11,25-diazapentacyclo[19.7.1.17,11.025,29.015,30]triacontane-8,22-dione
• CAS: 211759-06-7
• 化学式: C₂₈H₄₆N₂O₂
• 分子量: 442.685
• InChiKey: OHSAKPOEPCYGPC-DGOMJULGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.4
• 重原子数：
  32
• 可旋转键数：
  0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.93
• 拓扑面积：
  40.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  didemethylpetrosin D 、 碘甲烷 在 potassium carbonate 、 lithium diisopropyl amide 作用下， 生成 petrosin D
  参考文献：
  名称：

  Synthesis of Petrosins C and D

  摘要：

  Petrosins C and D (5 and 6), diastereomers of the known natural products petrosin (1), petrosin A (2), and petrosin B (3), have been prepared. The synthetic route involved initial creation of a 16-membered bis-pyridine intermediate, exemplified by compounds 7, 28, and 52. Several different methods for formation of the macrocycle were evaluated, and the most efficient (Schemes 7-9) involved use of Z double bonds in the six-carbon chains linking the two pyridine rings. This approach permitted the two pyridine subunits (37 and 39) to be joined by alkylation of a lithiated alpha-methylpyridine with an allylic chloride (e.g., 37 + 39 --> 40 and 49 --> 45). Bisannulation of compounds 7 and 28 was complicated by a surprising lack of acidity of the a-pyridyl methylene groups. Eventually, this problem was solved by stepwise introduction of two allyl groups, using the more acidic sulfone for introduction of the first (e.g., 52 --> 53) and direct allylation to introduce the second (e.g., 54 --> 55 + 56). The bisannulation was completed by hydroboration and conversion of the primary alcohols into methanesulfonate derivatives, which cyclized to afford bis-pyridinium derivatives. Reduction of these intermediate salts with sodium borohydride provided crystalline bis-enol ethers (60 and 63) and the relative configuration was established by single-crystal X-ray analysis of 63. After hydrolysis of the enol ethers to the corresponding ketones, the syntheses of 5 and 6 were completed by enolate methylation. As expected, compounds 5 and 6 do not form imine derivatives when treated with primary amines, presumably because of A(1,3) strain.

  DOI：

  10.1021/jo9801770
• 作为产物：
  描述：

  2-甲基-4-硝基吡啶-N-氧化物 在 2,6-二甲基吡啶 、 盐酸 、 sodium hydroxide 、 sodium tetrahydroborate 、 sodium dihydrogenphosphate 、 sodium amalgam 、 9-borabicyclo[3.3.1]nonane dimer 、 正丁基锂 、 ammonium molybdate 、 四甲基乙二胺 、 双氧水 、 仲丁基锂 、 sodium acetate 、 sodium hexamethyldisilazane 、 甲基磺酰氯 、 三乙胺 、 对甲苯磺酰肼 、 lithium chloride 、 三氯化磷 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 正己烷 、 氯仿 、 水 、 二甲基亚砜 为溶剂， 反应 149.5h， 生成 didemethylpetrosin D
  参考文献：
  名称：

  Synthesis of Petrosins C and D

  摘要：

  Petrosins C and D (5 and 6), diastereomers of the known natural products petrosin (1), petrosin A (2), and petrosin B (3), have been prepared. The synthetic route involved initial creation of a 16-membered bis-pyridine intermediate, exemplified by compounds 7, 28, and 52. Several different methods for formation of the macrocycle were evaluated, and the most efficient (Schemes 7-9) involved use of Z double bonds in the six-carbon chains linking the two pyridine rings. This approach permitted the two pyridine subunits (37 and 39) to be joined by alkylation of a lithiated alpha-methylpyridine with an allylic chloride (e.g., 37 + 39 --> 40 and 49 --> 45). Bisannulation of compounds 7 and 28 was complicated by a surprising lack of acidity of the a-pyridyl methylene groups. Eventually, this problem was solved by stepwise introduction of two allyl groups, using the more acidic sulfone for introduction of the first (e.g., 52 --> 53) and direct allylation to introduce the second (e.g., 54 --> 55 + 56). The bisannulation was completed by hydroboration and conversion of the primary alcohols into methanesulfonate derivatives, which cyclized to afford bis-pyridinium derivatives. Reduction of these intermediate salts with sodium borohydride provided crystalline bis-enol ethers (60 and 63) and the relative configuration was established by single-crystal X-ray analysis of 63. After hydrolysis of the enol ethers to the corresponding ketones, the syntheses of 5 and 6 were completed by enolate methylation. As expected, compounds 5 and 6 do not form imine derivatives when treated with primary amines, presumably because of A(1,3) strain.

  DOI：

  10.1021/jo9801770