(1R,3S,6S,7S,8S)-3,7-Dimethyl-11-oxa-tricyclo[6.2.1.0^1,6]undec-9-en-5-one | 158530-65-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 氧唑烯
• 英文名称: (1R,3S,6S,7S,8S)-3,7-Dimethyl-11-oxa-tricyclo[6.2.1.0^1,6]undec-9-en-5-one
• 英文别名: (1R,3S,6S,7S,8S)-3,7-dimethyl-11-oxatricyclo[6.2.1.01,6]undec-9-en-5-one
• CAS: 158530-65-5
• 化学式: C₁₂H₁₆O₂
• 分子量: 192.258
• InChiKey: DWMMGICHPVRACY-IXGYBFPHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  14
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  甲基锂 、 (1R,3S,6S,7S,8S)-3,7-Dimethyl-11-oxa-tricyclo[6.2.1.0^1,6]undec-9-en-5-one 以 乙二醇二甲醚 为溶剂， 反应 16.0h， 以74%的产率得到(1S,2R,4S,8S,9S,10S)-2,4,8,10-tetramethylbicyclo[4.4.0]dec-6-en-2,9-diol
  参考文献：
  名称：

  Thermodynamically controlled asymmetric induction: Applications with the intramolecular Diels-Alder reaction involving a furan diene

  摘要：

  Treatment of a variety of optically pure IMDAF precursors, containing one asymmetric centre on the sidearm, under thermodynamic conditions with MeAlCl(2) (-78 degrees C), provides cycloadducts with up to 5 asymmetric centres of known absolute stereochemistry. The minor cycloadduct can be equilibrated in the presence of MeAlCl(2) (-78 degrees C) to provide more of the major isomer. Treatment of the major cycloadduct with excess MeLi provides a decalin ring with up to 6 asymmetric centres, 5 of which are contiguous, in high enantiomeric excess.

  DOI：

  10.1016/0957-4166(94)80098-7
• 作为产物：
  描述：

  2-((S)-3-Iodo-2-methyl-propyl)-furan 在 Celite 、 叔丁基锂 、 甲基二氯化铝 、 silver carbonate 作用下， 以 苯 为溶剂， 反应 5.5h， 生成 (1R,3S,6S,7S,8S)-3,7-Dimethyl-11-oxa-tricyclo[6.2.1.0^1,6]undec-9-en-5-one
  参考文献：
  名称：

  Thermodynamically controlled asymmetric induction: Applications with the intramolecular Diels-Alder reaction involving a furan diene

  摘要：

  Treatment of a variety of optically pure IMDAF precursors, containing one asymmetric centre on the sidearm, under thermodynamic conditions with MeAlCl(2) (-78 degrees C), provides cycloadducts with up to 5 asymmetric centres of known absolute stereochemistry. The minor cycloadduct can be equilibrated in the presence of MeAlCl(2) (-78 degrees C) to provide more of the major isomer. Treatment of the major cycloadduct with excess MeLi provides a decalin ring with up to 6 asymmetric centres, 5 of which are contiguous, in high enantiomeric excess.

  DOI：

  10.1016/0957-4166(94)80098-7

文献信息

• Regio- and stereoselective ring openings of unsymmetrical oxatricyclo adducts
  作者：Simon Woo、Masood Parvez、Brian A. Keay

  DOI：10.1139/v97-081

  日期：1997.6.1

  S_N2′ ring-opening reactions of a number of substituted 11-oxatricyclo[6.2.1.0^1,6]undec-9-en-5-ones prepared via the intramolecular Diels–Alder reaction employing a furan diene (IMDAF) are reported. Primary, secondary, and tertiary organolithium reagents were capable of effecting the ring-opening reaction, while methyllithium required activation before any ring opening was observed. Hydride reagents, organocuprates, and Grignard reagents were generally ineffective. The ring-opening reaction was highly regio- and stereoselective for attack at C₉syn to the bridging oxygen atom provided that C₈ was not substituted. A highly stereoselective nucleophilic addition to the carbonyl group anti to the bridging oxygen was also observed. The high selectivity appears to be due to a combination of steric and electronic effects. Keywords: S_N2′ reactions, oxatricyclo adducts, Diels–Alder reaction, ring opening.

  报道了通过内分子Diels-Alder反应（IMDAF）采用呋喃二烯制备的一系列取代的11-氧杂三环[6.2.1.0^1,6]十一烯-5-酮的S_N2'环开反应。一级、二级和三级有机锂试剂均能引起环开反应，而甲基锂需要激活才能观察到任何环开。氢化试剂、有机铜试剂和格氏试剂通常无效。环开反应对于在C₈未被取代的情况下攻击C₉syn的桥氧原子具有高度的区域和立体选择性。也观察到了高度立体选择性的亲核加成到桥氧的对面的羰基上。高选择性似乎是由于立体和电子效应的组合。关键词：S_N2'反应、氧杂三环加合物、Diels-Alder反应、环开反应。