Perillyl benzoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: Perillyl benzoate
• 英文别名: 1-Cyclohexene-1-methanol, 4-(1-methylethenyl)-, benzoate；(4-prop-1-en-2-ylcyclohexen-1-yl)methyl benzoate
• 化学式: C₁₇H₂₀O₂
• 分子量: 256.345
• InChiKey: AKJMZNHWFFRVTF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.3
• 重原子数：
  19
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  Perillyl benzoate 、 硼氢化钠 生成 [4-(2-hydroxypropan-2-yl)cyclohexen-1-yl]methyl benzoate
  参考文献：
  名称：

  BEERLI, RENE;BORSCHBERG, HANS-JURG, HELV. CHIM. ACTA., 74,(1991) N, C. 110-116

  摘要：

  DOI：
• 作为产物：
  描述：

  紫苏醇 、 苯甲酰氯 在 三乙胺 作用下， 以 乙醚 为溶剂， 生成 Perillyl benzoate
  参考文献：
  名称：

  Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide

  摘要：

  A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields under 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA. The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of unsymmetrical allylic substrates. For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts. The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and gamma-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers. In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions. Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.

  DOI：

  10.1021/jo00110a047

文献信息

• 基于N-Boc酰胺底物的不饱和酯及其制备方法
  申请人：宁波工程学院

  公开号：CN117776925A

  公开（公告）日：2024-03-29

  本发明涉及一种基于N‑Boc酰胺底物的不饱和酯及其制备方法，本发明开创性的采用了一种无过渡金属催化的酰胺酯化反应，从不同取代官能团的N‑Boc酰胺出发，在温和的反应条件下，以无机碱代替贵金属催化剂，与不饱和醇发生亲核取代反应得到了不饱和酯类化合物；整个制备过程简单以实现，反应条件温和，反应产率高，并且反应产物在空气中稳定且易分离，对环境友好无污染。
• BEERLI, RENE;BORSCHBERG, HANS-JURG, HELV. CHIM. ACTA., 74,(1991) N, C. 110-116
  作者：BEERLI, RENE、BORSCHBERG, HANS-JURG

  DOI：——

  日期：——
• Unsymmetrical Ketone Synthesis via a Three-Component Connection Reaction of Organozincs, Allylating Agents, and Carbon Monoxide
  作者：Kengo Yasui、Keigo Fugami、Shuji Tanaka、Yoshinao Tamaru

  DOI：10.1021/jo00110a047

  日期：1995.3

  A wide variety of organozincs (diethylzinc, alkylzinc halides, and organozincs 2, 5, and 9a-e, functionalized with ester and nitrile groups) undergo a three-component connection reaction with carbon monoxide and allylic benzoates or phosphates 1a-h to furnish unsymmetrical ketones, e.g., 3, 6, and 10, in good yields under 1 atm of carbon monoxide at ambient temperature by the catalysis of tetrakis(triphenylphosphine)palladium in THF/HMPA. The regio- and stereoselectivities of the present carbonylation show marked contrast to those reported for the palladium-catalyzed carbonylation of unsymmetrical allylic substrates. For example, the reaction of crotyl benzoate with octylzinc iodide provides all the possible stereo- and regioisomers, i.e., cis- and trans-2-butenyl and 1-methyl-2-propenyl octyl ketones in comparable amounts. The carbonylative coupling of carvyl phosphates, trans- and cis-1h, and gamma-zincio ester 5 is stereospecific and proceeds with inversion of configuration at the allylic stereocenters to furnish cis- and trans-6h, respectively, as single diastereomers. In the absence of HMPA, the reaction feature changes dramatically and lactones 12 and 13 (composed of organozincs, carbon monoxide, and allylating agents in the ratios of 1:1:2 and 2:1:1, respectively) and symmetrical keto diesters 14 (composed of 2 mol of organozincs and 1 mol of carbon monoxide) are formed in varying ratios depending on the reaction conditions. Synthetic scope of the unsymmetrical ketones and mechanistic rationale for these unique and unprecedented reaction behaviors are discussed.