3-(tert-butyldimethylsiloxymethyl)cyclohex-2-en-1-one | 675107-24-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 3-(tert-butyldimethylsiloxymethyl)cyclohex-2-en-1-one
• 英文别名: 3-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclohex-2-en-1-one
• CAS: 675107-24-1
• 化学式: C₁₃H₂₄O₂Si
• 分子量: 240.418
• InChiKey: MUWKRIKBQODOEP-UHFFFAOYSA-N

物化性质

• 沸点：
  281.8±29.0 °C(Predicted)
• 密度：
  0.937±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.69
• 重原子数：
  16.0
• 可旋转键数：
  3.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  3-(tert-butyldimethylsiloxymethyl)cyclohex-2-en-1-one 在 二(氰基苯)二氯化钯 吡啶 、 三苯胂 、 四丁基氟化铵 、 碘 、 [双(三氟乙酰氧基)碘]苯 、 silver(l) oxide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 50.33h， 生成 3-hydroxymethyl-2-(1-propenyl)cyclohex-2-en-1-one
  参考文献：
  名称：

  Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

  摘要：

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.

  DOI：

  10.1021/jo0355303
• 作为产物：
  描述：

  3-phenylsulfinylmethylcyclohex-2-en-1-one 在 2,6-二甲基吡啶 、 4-二甲氨基吡啶 、 manganese(IV) oxide 、 sodium tetrahydroborate 、 cerium(III) chloride 、 三乙胺 、 三氟乙酸酐 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 13.0h， 生成 3-(tert-butyldimethylsiloxymethyl)cyclohex-2-en-1-one
  参考文献：
  名称：

  Different Reaction Modes for the Oxidative Dimerization of Epoxyquinols and Epoxyquinones. Importance of Intermolecular Hydrogen-Bonding

  摘要：

  An oxidative dimerization reaction, involving the three successive steps of oxidation, 6pi-electrocyclization, and Diels-Alder reaction, has been experimentally and theoretically investigated for the three 2-alkenyl-3-hydroxymethyl-2-cyclohexen-1-one derivatives epoxyquinol 3, epoxyquinone 6, and cyclohexenone 10. Of the sixteen possible modes of the oxidation/6pi-electrocylization/Diels-Alder reaction cascade for the epoxyquinone 6, and eight for the cyclohexenone 10, only the endo-anti(epoxide)-anti(Me)-hetero and endo-anti(Me)-hetero modes are, respectively, observed, while both endo-anti(epoxide)-anti(Me)-hetero and exo-anti(epoxide)-anti(Me)-homo reaction modes occur with the epoxyquinol 3. Intermolecular hydrogen-bonding is found to be the key cause of formation of both epoxyquinols A and B with 3, although epoxyquinone 6 and cyclohexenone 10 both gave selectively only the epoxyquinol A-type product. In the dimerization of epoxyquinol 3, two monomer 2H-pyrans 5 interact with each other to afford intermediate complex 28 or 29 stabilized by hydrogen-bonding, from which Diels-Alder reaction proceeds. Theoretical calculations have also revealed the differences in the reaction profiles of epoxyquinone 6 and cyclohexenone 10. Namely, the rate-determining step of the former is the Diels-Alder reaction, while that of the latter is the 6pi-electrocyclization.

  DOI：

  10.1021/jo0355303