(4aS,9S,14aS)-9-Methyl-octahydro-5,14-dioxa-8,11-dithia-benzocyclododecene-6,13-dione

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 大环内酯类和类似物
• 英文名称: (4aS,9S,14aS)-9-Methyl-octahydro-5,14-dioxa-8,11-dithia-benzocyclododecene-6,13-dione
• 化学式: C₁₃H₂₀O₄S₂
• 分子量: 304.431
• InChiKey: VNGRAIPPMIUKRS-DCAQKATOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.25
• 重原子数：
  19.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  52.6
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为产物：
  描述：

  trans-1,2-cyclohexandiol 在 三丙基硼烷 、 氧气 、 对甲苯磺酸 作用下， 以 甲醇 、 正己烷 、 苯 为溶剂， 生成 (4aS,9S,14aS)-9-Methyl-octahydro-5,14-dioxa-8,11-dithia-benzocyclododecene-6,13-dione
  参考文献：
  名称：

  Stereoselective free radical cycloaddition-macrocyclization in facile synthesis of trans-cyclohexano-fused 12-membered crown thioethers

  摘要：

  Homolytic cycloaddition of dithiols 1,2 derived from trans- and cis-1,2-cyclohexanediols to alkynes, induced by Pr3B-O-2, offers an extremely simple approach to trans- and cis-cyclohexano-fused 12-membered crown thialactones 4a-c-7a-c. The reaction of trans-1 proceeds with pronounced remote 1,6-asymmetric induction to give predominantly (IS*, 6R*, 12S*)-4a-c, while cis-2 reacts nonstereoselectively. Basing an molecular mechanics calculations the stereoselectivity is rationalized as a result of entropy favored pathway of macrocyclization.

  DOI：

  10.1016/0040-4020(95)00707-f

文献信息

• Remote asymmetric induction in free radical cycloaddition leading to trans-cyclohexano-fused 12-membered crown thioethers
  作者：Emmanuil I. Troyansky、Rustem F. Ismagilov、Yury A. Strelenko、Vyacheslav V. Samoshin、Dmitry V. Demchuk、Gennady I. Nikishin、Sergey V. Lindeman、Viktor V. Khrustalyov、Yury T. Struchkov

  DOI：10.1016/0040-4039(95)00287-5

  日期：1995.3

  Homolytic cycloaddition of dithiol 1, derived from trans-1,2-cyclohexanediol, to alkynes induced by Pr3BO2 occurs with 1,6-asymmetric induction to afford predominantly (1S∗, 6R∗, 12S∗)-trans-cyclohexano-fused 12-membered crown thialactones 4a-c. No pronounced diasteroselectivity was found in the corresponding reactions of dithiol 2, derived from cis-1,2-cyclohexanediol.

  二硫醇均裂环加成1，从反式-1,2-环己二醇衍生的，到Pr诱导炔3 BO 2与1,6-不对称诱导发生主要得到（1S *，6R *，12S *） -反式-环己基稠合的12元冠状内酯4a-c。在衍生自顺式1,2-环己二醇的二硫醇2的相应反应中未发现明显的非对映选择性。
• Stereoselective free radical cycloaddition-macrocyclization in facile synthesis of trans-cyclohexano-fused 12-membered crown thioethers
  作者：Emmanuil I. Troyansky、Rustem F. Ismagilov、Vyacheslav V. Samoshin、Yury A. Strelenko、Dmitry V. Demchuk、Gennady I. Nikishin、Sergey V. Lindeman、Viktor N. Khrustalyov、Yury T. Struchkov

  DOI：10.1016/0040-4020(95)00707-f

  日期：1995.10

  Homolytic cycloaddition of dithiols 1,2 derived from trans- and cis-1,2-cyclohexanediols to alkynes, induced by Pr3B-O-2, offers an extremely simple approach to trans- and cis-cyclohexano-fused 12-membered crown thialactones 4a-c-7a-c. The reaction of trans-1 proceeds with pronounced remote 1,6-asymmetric induction to give predominantly (IS*, 6R*, 12S*)-4a-c, while cis-2 reacts nonstereoselectively. Basing an molecular mechanics calculations the stereoselectivity is rationalized as a result of entropy favored pathway of macrocyclization.