(1R,1α,3α)-6,6-Dimethyl-4-<2-tert-butoxy-2-oxo-1-(phenylsulfonyl)ethyl>-3-oxabicyclo<3.1.0>hexan-2-one | 138336-34-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (1R,1α,3α)-6,6-Dimethyl-4-<2-tert-butoxy-2-oxo-1-(phenylsulfonyl)ethyl>-3-oxabicyclo<3.1.0>hexan-2-one
• CAS: 138336-34-2
• 化学式: C₁₉H₂₄O₆S
• 分子量: 380.462
• InChiKey: VOXXIUJYZQKAPT-DNDYEEKYSA-N

物化性质

• 沸点：
  555.1±46.0 °C(Predicted)
• 密度：
  1.248±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.37
• 重原子数：
  26.0
• 可旋转键数：
  4.0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  86.74
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  (1R,1α,3α)-6,6-Dimethyl-4-<2-tert-butoxy-2-oxo-1-(phenylsulfonyl)ethyl>-3-oxabicyclo<3.1.0>hexan-2-one 、 (S)-(3-苯氧基苯基)羟基乙腈 在 4-二甲氨基吡啶 、 N,N'-二环己基碳二亚胺 作用下， 以 二氯甲烷 为溶剂， 以76%的产率得到<1R,1α(S^*),3α(E)>-1-Cyano-1-(3-phenoxyphenyl)methyl 2,2-Dimethyl-3-<3-tert-butoxy-2-(phenylsulfonyl)-3-oxo-1-propenyl>cyclopropanecarboxylate
  参考文献：
  名称：

  A new way toward Z.alpha.,.beta. unsaturated esters: a pyrethroid application

  摘要：

  Use of the stereospecific condensation of beta-carbalkoxysulfones with aldehydes, followed by the stereospecific reduction of the afforded sulfonyl acrylate with sodium dithionite allows us to propose this method as a new way to prepare Z alpha,beta unsaturated esters. Steric hindrance seems to be the reason for the selectivity of the reduction and the mechanism was proved, by X-ray of an intermediate, to be a cis Michael addition of HSO2-, followed by an anti elimination of SO2 and the sulfinate group. This method discovered in the pyrethroid series for the synthesis of acrinathrin 1 could have general application.

  DOI：

  10.1021/jo00028a034
• 作为产物：
  描述：

  tert-butyl (phenylthio)acetate 在 四氢吡咯 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 生成 (1R,1α,3α)-6,6-Dimethyl-4-<2-tert-butoxy-2-oxo-1-(phenylsulfonyl)ethyl>-3-oxabicyclo<3.1.0>hexan-2-one
  参考文献：
  名称：

  A new way toward Z.alpha.,.beta. unsaturated esters: a pyrethroid application

  摘要：

  Use of the stereospecific condensation of beta-carbalkoxysulfones with aldehydes, followed by the stereospecific reduction of the afforded sulfonyl acrylate with sodium dithionite allows us to propose this method as a new way to prepare Z alpha,beta unsaturated esters. Steric hindrance seems to be the reason for the selectivity of the reduction and the mechanism was proved, by X-ray of an intermediate, to be a cis Michael addition of HSO2-, followed by an anti elimination of SO2 and the sulfinate group. This method discovered in the pyrethroid series for the synthesis of acrinathrin 1 could have general application.

  DOI：

  10.1021/jo00028a034