4,5-dimethyl-1,3,6,8-tetrahydrobenzo[c]naphtho[1'',2'':5',6']oxepino[3',4':5,6]benzo[3]oxepin

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 苯并噁庚英
• 英文名称: 4,5-dimethyl-1,3,6,8-tetrahydrobenzo[c]naphtho[1'',2'':5',6']oxepino[3',4':5,6]benzo[3]oxepin
• 英文别名: 16,17-Dimethyl-13,20-dioxahexacyclo[13.13.0.02,11.03,8.018,28.022,27]octacosa-1(15),2(11),3,5,7,9,16,18(28),22,24,26-undecaene
• 化学式: C₂₈H₂₄O₂
• 分子量: 392.497
• InChiKey: ASFCPQIZDRUGMI-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.6
• 重原子数：
  30
• 可旋转键数：
  0
• 环数：
  6.0
• sp3杂化的碳原子比例：
  0.21
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  2-[(But-2-yn-1-yloxy)methyl]-1-(2-{2-[(but-2-yn-1-yloxy)methyl]phenyl}ethyn-1-yl)naphthalene 在 carbon monoxide,cobalt,cyclopenta-1,3-diene 三苯基膦 作用下， 以 癸烷 为溶剂， 反应 2.0h， 以80%的产率得到4,5-dimethyl-1,3,6,8-tetrahydrobenzo[c]naphtho[1'',2'':5',6']oxepino[3',4':5,6]benzo[3]oxepin
  参考文献：
  名称：

  A Novel Strategy for the Synthesis of Molecules with Helical Chirality. Intramolecular [2 + 2 + 2] Cycloisomerization of Triynes under Cobalt Catalysis

  摘要：

  A straightforward synthetic approach to a new das's of molecules with helical chirality has been developed involving an intramolecular [2 + 2 + 2] cycloisomerization of triynes under CpCo(CO)(2)/ PPh3 catalysis. The cyclization reaction is promoted by visible light irradiation. Starting from 1,2-diarylacetylenes with two terminal or methyl-substituted tethered acetylene moieties (1a,b,4, 5, and 7), the target products (8a,b, 11, 12, and 14) are obtained in 64-89% yield. The triynes bearing terminal trimethylsilyl groups (Ic, 2, and 3) are less reactive and afford the products (8c, 9a,b, and 10) in 23-71% yield. The ability of the trimethylsilylated derivatives to cycloisomerize strongly depends on the tether length. The cyclized products (8-14) with five, six, and seven ortho-fused rings structurally resemble classical helicenes. Several representatives (8b, 11, 12, and 14) have been resolved into enantiomers by HPLC on a chiral column. Thus, the methodology exhibits a considerable versatility and allows the preparation of a variety of helical objects.

  DOI：

  10.1021/jo9801263

文献信息

• A Novel Strategy for the Synthesis of Molecules with Helical Chirality. Intramolecular [2 + 2 + 2] Cycloisomerization of Triynes under Cobalt Catalysis
  作者：Irena G. Stará、Ivo Starý、Adrian Kollárovič、Filip Teplý、David Šaman、Miloš Tichý

  DOI：10.1021/jo9801263

  日期：1998.6.1

  A straightforward synthetic approach to a new das's of molecules with helical chirality has been developed involving an intramolecular [2 + 2 + 2] cycloisomerization of triynes under CpCo(CO)(2)/ PPh3 catalysis. The cyclization reaction is promoted by visible light irradiation. Starting from 1,2-diarylacetylenes with two terminal or methyl-substituted tethered acetylene moieties (1a,b,4, 5, and 7), the target products (8a,b, 11, 12, and 14) are obtained in 64-89% yield. The triynes bearing terminal trimethylsilyl groups (Ic, 2, and 3) are less reactive and afford the products (8c, 9a,b, and 10) in 23-71% yield. The ability of the trimethylsilylated derivatives to cycloisomerize strongly depends on the tether length. The cyclized products (8-14) with five, six, and seven ortho-fused rings structurally resemble classical helicenes. Several representatives (8b, 11, 12, and 14) have been resolved into enantiomers by HPLC on a chiral column. Thus, the methodology exhibits a considerable versatility and allows the preparation of a variety of helical objects.