(Z)-2-(3-phenylthio-2-trimethylsilylmethylallyl)cyclohexanone | 117531-23-4

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (Z)-2-(3-phenylthio-2-trimethylsilylmethylallyl)cyclohexanone
• 英文别名: 2-[(Z)-3-phenylsulfanyl-2-(trimethylsilylmethyl)prop-2-enyl]cyclohexan-1-one
• CAS: 117531-23-4
• 化学式: C₁₉H₂₈OSSi
• 分子量: 332.582
• InChiKey: LBQHYJCLQBGVJN-PEZBUJJGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.15
• 重原子数：
  22.0
• 可旋转键数：
  6.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.53
• 拓扑面积：
  17.07
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为产物：
  描述：

  2-[(三甲基硅烷基)甲基]-2-丙烯-1-醇 在 氢氧化钾 、 三氟甲磺酸三甲基硅酯 、 双氧水 、 三乙胺 、 N,N-二异丙基乙胺 、 lithium chloride 作用下， 以 甲醇 、 二氯甲烷 、 水 、 溶剂黄146 、 N,N-二甲基甲酰胺 为溶剂， 反应 18.5h， 生成 (Z)-2-(3-phenylthio-2-trimethylsilylmethylallyl)cyclohexanone
  参考文献：
  名称：

  Allylation with Pummerer-generated substituted vinylthionium ions

  摘要：

  Pummerer-derived substituted vinylthionium ions (allyl phenyl sulfoxide, TMSOFf, EtN(i-Pr)(2), CH2Cl2, -78 degrees C) with a beta-trimethylsilylmethyl (2), gamma-phenyl (14), or gamma-phenylthio (15) group allylate the enol silyl ethers of acetophenone (3) and cyclohexanone (4) in good yield. Allylation with (14) and (15) required slow addition of base in order to limit the rate of production of intermediate, and thus avoid unwanted sila-Pummerer type products. Hunig's base conjugate addition was not observed in these cases. Both the (E)- and (Z)- forms of allyl sulfoxide (15) were shown to equilibrate to the (E)-transoid conformer prior to allylation resulting in exclusive (E)-vinyl sulfide formation. Blocking of the gamma-position resulted in preferential alpha- attack.

  DOI：

  10.1016/s0040-4020(01)85513-7

文献信息

• The scope of a new masked Michael reaction involving a Pummerer intermediate
  作者：Roger Hunter、Clive D. Simon

  DOI：10.1016/s0040-4039(00)86726-x

  日期：——
• Michael Joseph P., Simon Clive D., Walter Daryl S., Hunter Roger, Tetrahedron, 50 (1994) N 31, S 9365-9376
  作者：Michael Joseph P., Simon Clive D., Walter Daryl S., Hunter Roger

  DOI：——

  日期：——
• HUNTER, ROGER;SIMON, CLIVE D., TETRAHEDRON LETT., 29,(1988) N 18, 2257-2260
  作者：HUNTER, ROGER、SIMON, CLIVE D.

  DOI：——

  日期：——
• Allylation with Pummerer-generated substituted vinylthionium ions
  作者：Roger Hunter、Joseph P. Michael、Clive D. Simon、Daryl S. Walter

  DOI：10.1016/s0040-4020(01)85513-7

  日期：——

  Pummerer-derived substituted vinylthionium ions (allyl phenyl sulfoxide, TMSOFf, EtN(i-Pr)(2), CH2Cl2, -78 degrees C) with a beta-trimethylsilylmethyl (2), gamma-phenyl (14), or gamma-phenylthio (15) group allylate the enol silyl ethers of acetophenone (3) and cyclohexanone (4) in good yield. Allylation with (14) and (15) required slow addition of base in order to limit the rate of production of intermediate, and thus avoid unwanted sila-Pummerer type products. Hunig's base conjugate addition was not observed in these cases. Both the (E)- and (Z)- forms of allyl sulfoxide (15) were shown to equilibrate to the (E)-transoid conformer prior to allylation resulting in exclusive (E)-vinyl sulfide formation. Blocking of the gamma-position resulted in preferential alpha- attack.