3,3-dideuterio-1-octene | 150112-19-9

• 分子结构分类: 有机化合物 - 有机金属化合物
• 英文名称: 3,3-dideuterio-1-octene
• 英文别名: 3,3-d₂-oct-1-ene；3,3-dideuterio-oct-1-ene；3,3-Dideutero-octen-(1)
• CAS: 150112-19-9
• 化学式: C₈H₁₆
• 分子量: 114.199
• InChiKey: KWKAKUADMBZCLK-BFWBPSQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.14
• 重原子数：
  8.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  0.0
• 氢给体数：
  0.0
• 氢受体数：
  0.0

反应信息

• 作为反应物：
  描述：

  3,3-dideuterio-1-octene 、 苯甲酰氯 在 二氯二茂锆 、 magnesium 、 1,2-二溴乙烷 作用下， 以 四氢呋喃 、 苯 为溶剂， 反应 3.5h， 生成
  参考文献：
  名称：

  Transformation of Zirconocene−Olefin Complexes into Zirconocene Allyl Hydride and Their Use as Dual Nucleophilic Reagents:  Reactions with Acid Chloride and 1,4-Diketone

  摘要：

  Zirconocene-olefin complexes Cp2Zr(H2C=CHR), prepared in benzene-THF at 0 degreesC, react with acid chlorides to provide homoallylic alcohols. The key is an equilibrium between the zirconocene-olefin complexes and the corresponding zirconocene allyl hydride complexes via allylic C-H bond cleavage of the coordinating alkenes. Furthermore, the zirconocene-olefin complexes are also available for the reaction with 1,4-diketone to afford anti-1,4-diols with excellent diastereoselectivity. Thus, Cp2Zr(H2C CHR) serves as a donor of both hydride and an allylic group. These reactions also proceed efficiently by using zirconocene-olefin complexes, derived from Cp2ZrCl2, Mg metal, and 1-alkenes.

  DOI：

  10.1021/ja049184y
• 作为产物：
  描述：

  己酸甲酯 在 吡啶 、 lithium aluminium deuteride 、 magnesium 、 lithium bromide 作用下， 以 四氢呋喃 、 二氯甲烷 、 丙酮 为溶剂， 反应 49.0h， 生成 3,3-dideuterio-1-octene
  参考文献：
  名称：

  Transformation of Zirconocene−Olefin Complexes into Zirconocene Allyl Hydride and Their Use as Dual Nucleophilic Reagents:  Reactions with Acid Chloride and 1,4-Diketone

  摘要：

  Zirconocene-olefin complexes Cp2Zr(H2C=CHR), prepared in benzene-THF at 0 degreesC, react with acid chlorides to provide homoallylic alcohols. The key is an equilibrium between the zirconocene-olefin complexes and the corresponding zirconocene allyl hydride complexes via allylic C-H bond cleavage of the coordinating alkenes. Furthermore, the zirconocene-olefin complexes are also available for the reaction with 1,4-diketone to afford anti-1,4-diols with excellent diastereoselectivity. Thus, Cp2Zr(H2C CHR) serves as a donor of both hydride and an allylic group. These reactions also proceed efficiently by using zirconocene-olefin complexes, derived from Cp2ZrCl2, Mg metal, and 1-alkenes.

  DOI：

  10.1021/ja049184y

文献信息

• Mechanistic Study of a Re-Catalyzed Monoalkylation of Phenols
  作者：Dan Lehnherr、Xiao Wang、Feng Peng、Mikhail Reibarkh、Mark Weisel、Kevin M. Maloney

  DOI：10.1021/acs.organomet.8b00543

  日期：2019.1.14

  A mechanistic study of a rhenium catalyzed monoalkylation of phenols is described. Reaction kinetics reveals a zero-order dependence on both alkene and phenol and a half order dependence on catalyst. Isotopic labeling studies, competition experiments, kinetic isotope effects, and Hammett analysis together afford experimental data consistent with a reversible C–H activation step and an irreversible

  描述了of催化苯酚单烷基化的机理研究。反应动力学揭示了对烯烃和苯酚的零级依赖性和对催化剂的半级依赖性。同位素标记研究，竞争实验，动力学同位素效应和Hammett分析共同提供了与可逆CH活化步骤和不可逆加氢金属化过程一致的实验数据。限制周转的步骤被确定为催化剂的分解。催化剂和单一底物（烯烃或苯酚）的二元混合物以及反应混合物的NMR研究确定了潜在的中间体和非循环物种。尽管在这些混合物中形成了许多Re络合物，但整个反应既高收率，又对酚的单烷基化具有高度选择性。
• Conversion of Acid Chloride into Homoallylic Alcohol via Allylic C−H Bond Activation of Alkene with a Zirconocene Complex
  作者：Kazuya Fujita、Hideki Yorimitsu、Hiroshi Shinokubo、Seijiro Matsubara、Koichiro Oshima

  DOI：10.1021/ja0167194

  日期：2001.12.1