methyl 4-(1-hydroxy-2,2-dimethylbut-3-enyl)benzoate

• 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: methyl 4-(1-hydroxy-2,2-dimethylbut-3-enyl)benzoate
• 化学式: C₁₄H₁₈O₃
• 分子量: 234.295
• InChiKey: GQIQVQWNVKSWKW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  17
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  46.5
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  3-甲基-1,2-丁二烯 、 对甲酰基苯甲酸甲酯 在 [Ir(cod)BIPHEP]B(3,5-(CF₃)2C₆H₃)4 氢气 、 lithium carbonate 作用下， 以 乙酸乙酯 、 1,2-二氯乙烷 为溶剂， 60.0 ℃ 、101.33 kPa 条件下， 反应 10.0h， 以69%的产率得到methyl 4-(1-hydroxy-2,2-dimethylbut-3-enyl)benzoate
  参考文献：
  名称：

  Carbonyl Allylation in the Absence of Preformed Allyl Metal Reagents:  Reverse Prenylation via Iridium-Catalyzed Hydrogenative Coupling of Dimethylallene

  摘要：

  Iridium-catalyzed hydrogenation of dimethylallene in the presence of aromatic, heteroaromatic, and aliphatic carbonyl electrophiles 1a-12a delivers products of reverse prenylation 1b-12b. Reductive coupling of dimethyl allene to aldehyde 8a under an atmosphere of deuterium provides deuterio -8b. As revealed by H-2 NMR analysis, deuterium incorporation is observed at the vinylic position (80% H-2). Unlike established methods for carbonyl allylation, the present protocol circumvents the use of stoichiometrically preformed organometallic reagents.

  DOI：

  10.1021/ja075971u

文献信息

• Palladium-catalysed carbonyl allylation by isoprene via regioselective 1,4-addition of tin hydride formed in situ
  作者：Yoshiro Masuyama、Megumi Tsunoda、Yasuhiko Kurusu

  DOI：10.1039/c39940001451

  日期：——

  Isoprene reacts with aldehydes in the presence of a catalytic amount of Pd(OAc)2–4PPh3 or Pd(PPh3)4 and a stoichiometric amount of SnCl2 at 40–50 °C in AcOH–H2O to produce 1-substituted 2,2-dimethyl-3-buten-1-ols regioselectively.

  异戊二烯在催化剂Pd(OAc)2-4PPh3或Pd(PPh3)4和等摩尔量的SnCl2存在下，于40-50°C的乙酸-水溶液中与醛类反应，选择性地生成1-取代的2,2-二甲基-3-丁烯-1-醇。
• Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis
  作者：Xian‐Wang Zeng、Jia‐Ni Lin、Wei Shu

  DOI：10.1002/anie.202403073

  日期：2024.6.3

  Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with the control of enantioselectivity to access different regio‐ and enantiomers by switching the least reaction parameters are one of the most attractive ways in organic synthesis, which provide access to diverse enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent and enantioselective reductive hydroalkylation of 1,3‐dienes with aldehydes have been achieved, furnishing different enantioenriched homoallylic alcohol architectures in good levels of enantioselectivity. The reaction features the switch of regioselectivity tuned by the selection of proton source. The use of an acid as proton source provided asymmetric 1,2‐hydroalkylation products under reductive conditions, yet asymmetric 4,3‐hydroalkylation products were obtained with silane as hydride source. This catalytic protocol allows for the access of homoallylic alcohols with two continuous saturated carbon centers in good levels of regio‐, diastereo‐, and enantioselectivity.