syn-2-(Methylthio)bicyclo<4.1.0>heptane

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: syn-2-(Methylthio)bicyclo<4.1.0>heptane
• 英文别名: syn-2-(Methylthio)bicyclo[4.1.0]heptane；(1S,2R,6R)-2-methylsulfanylbicyclo[4.1.0]heptane
• 化学式: C₈H₁₄S
• 分子量: 142.265
• InChiKey: ANQLTRJOFFOXDR-GJMOJQLCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为产物：
  描述：

  2-环己烯醇 在 lithium aluminium tetrahydride 、 偶氮二甲酸二异丙酯 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 、 三苯基膦 作用下， 以 乙醚 、 萘烷 、 正戊烷 、 苯 为溶剂， 反应 24.75h， 生成 syn-2-(Methylthio)bicyclo<4.1.0>heptane
  参考文献：
  名称：

  Stereodirecting effect of a substrate methoxy substituent on the addition of singlet methylene to a double bond

  摘要：

  The stereodirecting effects of substrate methoxy, hydroxy, methylthio, and methyl substituents were examined in the addition of 1:CH2 to the double bonds of substrates 1a-d. The carbene, generated by photolysis of CH2N2, inserted into the C-H bonds of solvent and substrate, added to the substrate double bond to give products 2a-d, and attacked the oxygen or sulfur atom of substrates 1a-c to produce ylide intermediates which underwent 2,3-sigmatropic rearrangement to give products 3a-c. A preference for addition syn to the methoxy group of substrate 1a was observed when the reaction was run in pentane solution (syn-2a/anti-2a, 1.14 +/- 0.02), while a preference for formation of anti-2a was observed in diethyl ether solution (syn-2a/anti-2a, 0.92 +/- 0.03). A preference for 1:CH2 addition anti to the substrate substituent was observed for substrates 1b-d in both pentane and ether solution. The effect of the methoxy substituent was also examined in the addition of 1:CH2 to syn-7-methoxynorbornene (5b). Explanations for the substituent effects are offered based on both steric hindrance and interaction between 1:CH2 and the substituent, including formation and subsequent reaction of the ylide intermediates.

  DOI：

  10.1021/jo00075a016

文献信息

• Stereodirecting effect of a substrate methoxy substituent on the addition of singlet methylene to a double bond
  作者：Terry A. Young、Colleen O'Rourke、Nathan B. Gray、Brian D. Lewis、Curt A. Dvorak、Kan Shuh Kuen、JoAnn P. DeLuca

  DOI：10.1021/jo00075a016

  日期：1993.11

  The stereodirecting effects of substrate methoxy, hydroxy, methylthio, and methyl substituents were examined in the addition of 1:CH2 to the double bonds of substrates 1a-d. The carbene, generated by photolysis of CH2N2, inserted into the C-H bonds of solvent and substrate, added to the substrate double bond to give products 2a-d, and attacked the oxygen or sulfur atom of substrates 1a-c to produce ylide intermediates which underwent 2,3-sigmatropic rearrangement to give products 3a-c. A preference for addition syn to the methoxy group of substrate 1a was observed when the reaction was run in pentane solution (syn-2a/anti-2a, 1.14 +/- 0.02), while a preference for formation of anti-2a was observed in diethyl ether solution (syn-2a/anti-2a, 0.92 +/- 0.03). A preference for 1:CH2 addition anti to the substrate substituent was observed for substrates 1b-d in both pentane and ether solution. The effect of the methoxy substituent was also examined in the addition of 1:CH2 to syn-7-methoxynorbornene (5b). Explanations for the substituent effects are offered based on both steric hindrance and interaction between 1:CH2 and the substituent, including formation and subsequent reaction of the ylide intermediates.