3-(tert-butyl-dimethyl-silanyloxymethyl)-cyclohex-2-enol | 675107-23-0

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: 3-(tert-butyl-dimethyl-silanyloxymethyl)-cyclohex-2-enol
• 英文别名: 3-[[Tert-butyl(dimethyl)silyl]oxymethyl]cyclohex-2-en-1-ol
• CAS: 675107-23-0
• 化学式: C₁₃H₂₆O₂Si
• 分子量: 242.434
• InChiKey: DGCJVKWQPUSYQV-UHFFFAOYSA-N

物化性质

• 沸点：
  281.6±33.0 °C(Predicted)
• 密度：
  0.943±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.48
• 重原子数：
  16
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.85
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  3-(tert-butyl-dimethyl-silanyloxymethyl)-cyclohex-2-enol 在 二(氰基苯)二氯化钯 吡啶 、 manganese(IV) oxide 、 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 54.33h， 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 、 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 9.0h， 生成 3-(tert-butyl-dimethyl-silanyloxymethyl)-cyclohex-2-enol
  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

文献信息

• SUBSTITUTED FLUOROETHYL UREAS AS ALPHA 2 ADRENERGIC AGENTS
  申请人：Chow Ken

  公开号：US20080255239A1

  公开（公告）日：2008-10-16

  Therapeutic compounds, and methods, compositions, and medicaments related thereto are disclosed herein.

  本文揭示了治疗化合物、方法、组合物和相关药物。
• Regio- and Stereoselective Addition of HO/OOH to Allylic Alcohols
  作者：Xiao-Tao Wang、Wei-Bo Han、Hui-Jun Chen、Qinghong Zha、Yikang Wu

  DOI：10.1021/acs.joc.0c01280

  日期：2020.8.7

  readily react with ethereal H2O2 in the presence of catalytic amounts of Na2MoO4-gly or MoO2(acac)2, affording the C═C trans hydroxylation–hydroperoxylation products in good yields with high regio- and stereoselectivity. Use of enantiomers of cyclic substrates resulted in corresponding enantiopure diol-tert-hydroperoxides. The possibility of further conversion of the diol-tert-hydroperoxides into triols

  在催化量的Na 2 MoO 4 -gly或MoO 2（acac）2的存在下，一系列烯丙醇易于与醚H 2 O 2反应，从而以高收率提供C═C反羟基化-氢过氧化产物具有高区域选择性和立体选择性。使用环状底物的对映异构体产生相应的对映体纯的二醇-叔氢过氧化物。还举例说明了将二醇-叔氢过氧化物进一步转化为具有包含季中心的分离的叔-过氧基团的三醇或线性结构单元的可能性。