(1RS,2SR,8RS,9SR)-2,8-dimethylbicyclo[4.4.4.0]dec-6-en-2,9-diol | 142286-92-8

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1RS,2SR,8RS,9SR)-2,8-dimethylbicyclo[4.4.4.0]dec-6-en-2,9-diol
• 英文别名: (1S,6R,7S,8aR)-1,6-dimethyl-3,4,6,7,8,8a-hexahydro-2H-naphthalene-1,7-diol
• CAS: 142286-92-8
• 化学式: C₁₂H₂₀O₂
• 分子量: 196.29
• InChiKey: VSPJNUSQQJKULM-YJQGPUDQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.86
• 重原子数：
  14.0
• 可旋转键数：
  0.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  40.46
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  甲基锂 、 (6α,8α-H)-11-oxatricyclo[6.2.1.0^1,6]undec-9-en-5-one 在 四甲基乙二胺 作用下， 以 乙醚 为溶剂， 以33%的产率得到(1RS,5RS,6RS,8RS)-5-methyl-11-oxatricyclo[6.2.1.0^1,6]undec-9-en-5-ol
  参考文献：
  名称：

  Regio- and stereo-selective SN2′ ring openings of substituted 11-oxatricyclo[6.2.1.01,6]undec-9-en-5-ones

  摘要：

  Various substituted 11-oxatricyclo[6.2.1.0(1,6)]undec-9-en-5-ones undergo regio- and stereo-selective S(N)2' ring openings to provide products with up to five (5) contiguous asymmetric centres of known relative stereochemistry.

  DOI：

  10.1016/s0040-4039(00)79051-4

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。