(3aR,9S,9aR)-9-Chloro-3-oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester | 141726-59-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 菲及其衍生物
• 英文名称: (3aR,9S,9aR)-9-Chloro-3-oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester
• 英文别名: ethyl (3aR,4S,9aR)-4-chloro-1-oxo-3,3a,4,9-tetrahydro-2H-cyclopenta[b]naphthalene-9a-carboxylate
• CAS: 141726-59-2
• 化学式: C₁₆H₁₇ClO₃
• 分子量: 292.762
• InChiKey: QURONJOTWWQDMM-JGGQBBKZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  20
• 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 manganese triacetate 作用下， 以 溶剂黄146 为溶剂， 反应 20.0h， 生成 (3aR,9aS)-9-Chloro-3-oxo-1,2,3,4,9,9a-hexahydro-cyclopenta[b]naphthalene-3a-carboxylic acid ethyl ester 、 (3aR,9S,9aR)-9-Chloro-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