((R)-1-propa-1,2-dienyloxy-ethyl)-benzene | 1019841-97-4

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ((R)-1-propa-1,2-dienyloxy-ethyl)-benzene
• CAS: 1019841-97-4
• 化学式: C₁₁H₁₂O
• 分子量: 160.216
• InChiKey: AXKGYJVRRAZMEY-SNVBAGLBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  9.2
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  环丁酮 、 ((R)-1-propa-1,2-dienyloxy-ethyl)-benzene 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 1.0h， 以92%的产率得到1-[1-(1-(R)-phenyl-ethoxy)-propa-1,2-dienyl]-cyclobutanol
  参考文献：
  名称：

  Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

  摘要：

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.

  DOI：

  10.1021/ja7111299
• 作为产物：
  描述：

  (R)-1-(prop-2-ynyloxy)-ethyl benzene 在 potassium tert-butylate 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以70%的产率得到((R)-1-propa-1,2-dienyloxy-ethyl)-benzene
  参考文献：
  名称：

  Palladium-Catalyzed Diastereo- and Enantioselective Wagner−Meerwein Shift: Control of Absolute Stereochemistry in the C−C Bond Migration Event

  摘要：

  Inducing absolute stereochemistry in Wagner-Meerwein shifts was examined in a ring expansion protocol. Initiated by generation of a pi-allylpalladium intermediate by hydropalladation of allenes, the ring expansion of allenylcyclobutanol substrates proceeded with excellent diastereo- and enantioselectivities. The results demonstrate that, during the C-C bond migration process, our chiral catalysts can control the stereochemistry of both the pi-allylpalladium intermediate and the corresponding migration bond. Moreover, the stereochemical outcome of the reaction can be rationalized very well with the working model of the chiral catalyst. The method provides an efficient way to synthesize highly substituted cyclopentanones with an alpha-chiral O-tertiary center which has various synthetic applications.

  DOI：

  10.1021/ja7111299

文献信息

• Photochemical Asymmetric Palladium-Catalyzed Allylation Reaction: Expeditious Entry to Chiral 1,2-Amino Alcohols and 1,2-Diamines
  作者：Hui Xie、Haohua Chen、Uttam Dutta、Yu Lan、Bernhard Breit

  DOI：10.1021/acscatal.4c04209

  日期：2024.9.6

  alcohols and 1,2-diamines via the asymmetric allylation of α-silyl amines with heteroatom-substituted allenes and 1,3-dienes. This protocol is characterized by its mild conditions, high regio- and enantioselectivities, and wide substrate scope, including aliphatic amines or N-heterocyclic substrates especially. Computational and experimental mechanistic studies indicate that the reaction proceeds through

  多种烷基胺的构建对于药物发现和天然产物合成具有重要意义。在此，我们报道了一种有效的光氧化还原/钯双重催化，通过α-甲硅烷基胺与杂原子取代的丙二烯和1,3-二烯的不对称烯丙基化来构建受保护的1,2-氨基醇和1,2-二胺。该方案的特点是条件温和、区域选择性和对映选择性高、底物范围广，特别是脂肪胺或N-杂环底物。计算和实验机理研究表明，该反应通过PPTS对Pd(0)催化剂进行氧化加成、丙二烯插入、外层自由基取代型C-C键形成以及Pd(I)还原的顺序进行。红外光（II）。其中，外球自由基取代是对映体和区域选择性的决定步骤。