(3aR,9aS)-3-Oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester | 112293-00-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 萘
• 英文名称: (3aR,9aS)-3-Oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester
• 英文别名: ethyl (3aR,9aS)-3-oxo-2,4,9,9a-tetrahydro-1H-cyclopenta[b]naphthalene-3a-carboxylate
• CAS: 112293-00-2
• 化学式: C₁₆H₁₈O₃
• 分子量: 258.317
• InChiKey: HQOWWPZJROAGDA-XJKSGUPXSA-N

物化性质

• 沸点：
  385.7±42.0 °C(Predicted)
• 密度：
  1.196±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  19
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  Ethyl 2-benzyl-7-chloro-3-oxohept-6-enoate 在 palladium on activated charcoal 氢气 、 manganese triacetate 作用下， 生成 (3aR,9aS)-3-Oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester 、 (3aR,9aR)-3-Oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester
  参考文献：
  名称：

  Control of the regioselectivity of oxidative free-radical cyclizations by addition to haloalkenes

  摘要：

  Chlorine substituents on the alkene control the regioselectivity of the cyclization of 5-hexenyl or 6-heptenyl radicals generated by oxidation of an acetoacetate ester or 1,3-diketone with Mn(OAc)3.2H2O. 6-Exo-cyclization of the radicals obtained by oxidation of benzoylacetone derivatives 10 and 13, containing a chlorine on the terminal double bond carbon, gives alpha-chloroalkyl radicals that add to the aromatic ring to give 11 and 16, respectively. Loss of HCl leads to naphthols 8 and 17 indicating that this reaction may be useful for aureolic acid synthesis. Exo-cyclization is the exclusive process with acetoacetates 28b, 44, 55b, and 59 containing a chlorine on the terminal double bond carbon. 6-Endo-cyclization is the exclusive process with acetoacetates 18c and 51b containing a chlorine on the internal double bond carbon. Intra- and intermolecular competition experiments indicate that these effects are primarily steric. The chlorine substituent controls the regioselectivity of the cyclization by sterically hindering attack of the radical on the chlorine bearing double bond carbon thereby retarding formation of the beta-chloroalkyl radical. The chlorine substituent does not electronically accelerate attack on the other end of the double bond to give the alpha-chloroalkyl radical.

  DOI：

  10.1021/jo00041a026

文献信息

• Manganese (III) based oxidative free-radical cyclizations. 3. Polycyclization reactions proceeding through secondary radicals.
  作者：Raju Mohan、Steven A. Kates、Mark A. Dombroski、Barry B. Snider

  DOI：10.1016/s0040-4039(01)81004-2

  日期：1987.1

  Oxidative cyclizations of 3, 14, 18 and 21 with Mn(OAc)3 ·2H2O give the tricyclic products 6, 15, 19 and 23, respectively, in good yield. These reactions proceed through a monocyclic secondary radical which adds to the benzene ring prior to the second oxidation.

  的氧化环化3，14，18和21用的Mn（OAc）3 ·2H 2 ö得到三环产品6，15，19和23分别，以良好的收率。这些反应通过单环仲自由基进行，该仲环自由基在第二次氧化之前加到苯环上。
• MOHAN RAJU; KATES S. A.; DOMBROSKI M. A.; SNIDER B. B., TETRAHEDRON LETT., 28,(1987) N 8, 845-848
  作者：MOHAN RAJU、 KATES S. A.、 DOMBROSKI M. A.、 SNIDER B. B.

  DOI：——

  日期：——