2-<(Methanesulfonyl)oxy>-1-acetylcyclohexene | 132079-92-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磺酸及其衍生物
• 英文名称: 2-<(Methanesulfonyl)oxy>-1-acetylcyclohexene
• 英文别名: 2-(methanesulfonyloxy)-1-acetylcyclohexene；(2-Acetylcyclohexen-1-yl) methanesulfonate
• CAS: 132079-92-6
• 化学式: C₉H₁₄O₄S
• 分子量: 218.274
• InChiKey: IAZFVLXHUDIPOQ-UHFFFAOYSA-N

物化性质

• 沸点：
  366.5±42.0 °C(Predicted)
• 密度：
  1.24±0.1 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  0.9
• 重原子数：
  14
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  68.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (E)-1-phenyl-(2-tributylstannyl)ethene 、 2-<(Methanesulfonyl)oxy>-1-acetylcyclohexene 在 四(三苯基膦)钯 lithium bromide 作用下， 以 四氢呋喃 为溶剂， 反应 36.0h， 以57%的产率得到1-acetyl-2-((E)-2-phenyl-1-ethenyl)cyclohexene
  参考文献：
  名称：

  Palladium-catalyzed cross-coupling of .beta.-(methanesulfonyl)oxyenones with organostannanes

  摘要：

  beta-(Methanesulfonyl)oxy enones, derived from 1,3-diones, cross-couple with vinylstannanes in 50-80% yields when a substoichiometric amount of Pd(PPh3)4 and stoichiometric lithium bromide are used. Phenyltributylstannane affords low yields of cross-coupled product. Tetrabutyltin, tributyltin hydride, and ethynyltributyltin do not couple under the reaction conditions. The reaction is proposed to involve in situ formation of the beta-bromo enone, oxidative addition to the Pd(0) catalyst, transmetalation, and reductive elimination to afford cross-coupled products. The analogous enol phosphates undergo coupling in low yields, the major product resulting from regeneration of the 1,3-dione.

  DOI：

  10.1021/jo00004a028
• 作为产物：
  描述：

  2-乙酰基环己酮 、 甲基磺酰氯 在 三乙胺 作用下， 以 乙二醇二甲醚 为溶剂， 反应 12.0h， 以70%的产率得到2-<(Methanesulfonyl)oxy>-1-acetylcyclohexene
  参考文献：
  名称：

  Palladium-catalyzed cross-coupling of .beta.-(methanesulfonyl)oxyenones with organostannanes

  摘要：

  beta-(Methanesulfonyl)oxy enones, derived from 1,3-diones, cross-couple with vinylstannanes in 50-80% yields when a substoichiometric amount of Pd(PPh3)4 and stoichiometric lithium bromide are used. Phenyltributylstannane affords low yields of cross-coupled product. Tetrabutyltin, tributyltin hydride, and ethynyltributyltin do not couple under the reaction conditions. The reaction is proposed to involve in situ formation of the beta-bromo enone, oxidative addition to the Pd(0) catalyst, transmetalation, and reductive elimination to afford cross-coupled products. The analogous enol phosphates undergo coupling in low yields, the major product resulting from regeneration of the 1,3-dione.

  DOI：

  10.1021/jo00004a028

文献信息

• Preparation and reactivity of functionalized alkenyl-zinc, -copper, and -chromium organometallics
  作者：Paul Knochel、C. Janakiram Rao

  DOI：10.1016/s0040-4020(01)80504-4

  日期：1993.1

  Beta-halogeno-alpha,beta-unsaturated carbonyl derivatives were converted to the corresponding zinc organometallics 2a under mild conditions in THF (Zn dust, 25-45-degrees-C, 1-4h). These functionalized alkenylzinc iodides react with a variety of alkenyl and aromatic iodides affording the desired coupling products in 40-97% yield. The addition of a THF solution of CuCN.2LiCl to 2a affords the corresponding organocopper derivatives 2b which react with electrophiles, such as alkynyl and allylic halides, nitro olefins, enones, and chlorotrimethylstannane providing polyfunctional unsaturated carbonyl compounds in 71-95% yield. The insertion of chromium (II) chloride to beta-iodo and to some beta-(p-tosyl)enones in DMF furnishes new functionalized chromium (III) organometallics 2c which react with aldehydes providing gamma-hydroxy unsaturated carbonyl derivatives in 40-91% yield. The synthetic scope and the limitations of this methodology are discussed.