(1S,6S,8R,12R,13R)-12-hydroxy-7,7,14,14-tetramethylpentacyclo[11.1.1.16,8.02,11.05,10]hexadeca-2(11),3,5(10)-trien-9-one | 170902-00-8

• 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: (1S,6S,8R,12R,13R)-12-hydroxy-7,7,14,14-tetramethylpentacyclo[11.1.1.16,8.02,11.05,10]hexadeca-2(11),3,5(10)-trien-9-one
• CAS: 170902-00-8
• 化学式: C₂₀H₂₄O₂
• 分子量: 296.409
• InChiKey: KDUJQKCPUWCTQO-NLIDSEJHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  22
• 可旋转键数：
  0
• 环数：
  7.0
• sp3杂化的碳原子比例：
  0.65
• 拓扑面积：
  37.3
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1S,6S,8R,12R,13R)-12-hydroxy-7,7,14,14-tetramethylpentacyclo[11.1.1.16,8.02,11.05,10]hexadeca-2(11),3,5(10)-trien-9-one 在 4 A molecular sieve 、 pyridinium chlorochromate 作用下， 以 二氯甲烷 为溶剂， 反应 72.0h， 以93%的产率得到(1S,3R,6R,8S)-1,2,3,6,7,8-Hexahydro-2,2,7,7-tetramethyl-1,3:6,8-dimethanophenathrene-4,5-dione
  参考文献：
  名称：

  Oxidative Coupling of the Enolate Anion of (1R)-(+)-Verbenone with Fe(III) and Cu(II) Salts. Two Modes of Conjoining This Bicyclic Ketone across a Benzene Ring

  摘要：

  The regioselectivity of the oxidative coupling of the enolate anion of (1R)-(+)-verbenone (97% ee) has been examined with CuCl2 and FeCl3 as catalysts. With Cu(II), selective formation of the gamma,gamma-product is observed. An increase in temperature above -40 degrees C results in further oxidation of the intra-ring ethano bridge to a trans double bond, provided that excess LDA has been added. In the presence of Fe(III), the coupling is partially diverted to the alpha,gamma-product, which has proven amenable to direct conversion to that C-2-symmetric ''dimer'' having the carbonyl groups in a para relationship. The second C-2 ''dimer'' featuring meta orientation of the ketone functionalities has been conveniently prepared from the trienedione or its derived diol by thermal or photochemical trans --> cis equilibration, thermal 6 pi electrocyclization with concurrent aromatization, and PCC oxidation. Some potential applications of this conformationally rigid benzenoid system to enantioselective synthesis are outlined.

  DOI：

  10.1021/jo00127a037
• 作为产物：
  描述：

  马鞭草烯酮 在 六甲基磷酰三胺 、 manganese(IV) oxide 、 正丁基锂 、 三氯化铁 、 二异丁基氢化铝 、 二异丙胺 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 27.25h， 生成 (1S,6S,8R,12R,13R)-12-hydroxy-7,7,14,14-tetramethylpentacyclo[11.1.1.16,8.02,11.05,10]hexadeca-2(11),3,5(10)-trien-9-one
  参考文献：
  名称：

  Oxidative Coupling of the Enolate Anion of (1R)-(+)-Verbenone with Fe(III) and Cu(II) Salts. Two Modes of Conjoining This Bicyclic Ketone across a Benzene Ring

  摘要：

  The regioselectivity of the oxidative coupling of the enolate anion of (1R)-(+)-verbenone (97% ee) has been examined with CuCl2 and FeCl3 as catalysts. With Cu(II), selective formation of the gamma,gamma-product is observed. An increase in temperature above -40 degrees C results in further oxidation of the intra-ring ethano bridge to a trans double bond, provided that excess LDA has been added. In the presence of Fe(III), the coupling is partially diverted to the alpha,gamma-product, which has proven amenable to direct conversion to that C-2-symmetric ''dimer'' having the carbonyl groups in a para relationship. The second C-2 ''dimer'' featuring meta orientation of the ketone functionalities has been conveniently prepared from the trienedione or its derived diol by thermal or photochemical trans --> cis equilibration, thermal 6 pi electrocyclization with concurrent aromatization, and PCC oxidation. Some potential applications of this conformationally rigid benzenoid system to enantioselective synthesis are outlined.

  DOI：

  10.1021/jo00127a037

文献信息

• Oxidative Coupling of the Enolate Anion of (1R)-(+)-Verbenone with Fe(III) and Cu(II) Salts. Two Modes of Conjoining This Bicyclic Ketone across a Benzene Ring
  作者：Leo A. Paquette、Eugene I. Bzowej、Bruce M. Branan、Kenetha J. Stanton

  DOI：10.1021/jo00127a037

  日期：1995.11

  The regioselectivity of the oxidative coupling of the enolate anion of (1R)-(+)-verbenone (97% ee) has been examined with CuCl2 and FeCl3 as catalysts. With Cu(II), selective formation of the gamma,gamma-product is observed. An increase in temperature above -40 degrees C results in further oxidation of the intra-ring ethano bridge to a trans double bond, provided that excess LDA has been added. In the presence of Fe(III), the coupling is partially diverted to the alpha,gamma-product, which has proven amenable to direct conversion to that C-2-symmetric ''dimer'' having the carbonyl groups in a para relationship. The second C-2 ''dimer'' featuring meta orientation of the ketone functionalities has been conveniently prepared from the trienedione or its derived diol by thermal or photochemical trans --> cis equilibration, thermal 6 pi electrocyclization with concurrent aromatization, and PCC oxidation. Some potential applications of this conformationally rigid benzenoid system to enantioselective synthesis are outlined.