(4E,16E)-12,24-Dimethoxy-9,21-diaza-tricyclo[18.4.0.0^8,13]tetracosa-1(24),4,8,10,12,16,20,22-octaene | 211758-70-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (4E,16E)-12,24-Dimethoxy-9,21-diaza-tricyclo[18.4.0.0^8,13]tetracosa-1(24),4,8,10,12,16,20,22-octaene
• 英文别名: (4E,16E)-12,24-dimethoxy-9,21-diazatricyclo[18.4.0.08,13]tetracosa-1(24),4,8,10,12,16,20,22-octaene
• CAS: 211758-70-2
• 化学式: C₂₄H₃₀N₂O₂
• 分子量: 378.514
• InChiKey: AWFDDJPGJSYYPM-GGWOSOGESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.1
• 重原子数：
  28
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  44.2
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (4E,16E)-12,24-Dimethoxy-9,21-diaza-tricyclo[18.4.0.0^8,13]tetracosa-1(24),4,8,10,12,16,20,22-octaene 在 L-Selectride 作用下， 以 四氢呋喃 为溶剂， 反应 2.5h， 生成 (3E,15E)-8-methoxy-11,23-diazatetracyclo[17.7.1.07,12.023,27]heptacosa-3,7,9,11,15,19(27)-hexaen-20-one
  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：

  2,2-Dimethyl-propionic acid 1-(2-{2-[(E)-6-(2-benzenesulfonylmethyl-4-methoxy-pyridin-3-yl)-hex-3-enyl]-4-methoxy-pyridin-3-yl}-ethyl)-allyl ester 在 tris(dibenzylideneacetone)dipalladium(0) chloroform complex 、 sodium hexamethyldisilazane 、 氢化铝 、 1,2-双(二苯基膦)乙烷 、 mercury dichloride 作用下， 以 四氢呋喃 为溶剂， 反应 9.0h， 生成 (4E,16E)-12,24-Dimethoxy-9,21-diaza-tricyclo[18.4.0.0^8,13]tetracosa-1(24),4,8,10,12,16,20,22-octaene
  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

文献信息

• Synthesis of Petrosins C and D
  作者：Clayton H. Heathcock、Richard C. D. Brown、Thea C. Norman

  DOI：10.1021/jo9801770

  日期：1998.7.1

  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.