phenyl 4,8-dimethyl-3,7-nonadienethioate

• 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: phenyl 4,8-dimethyl-3,7-nonadienethioate
• 英文别名: S-phenyl (3E)-4,8-dimethylnona-3,7-dienethioate
• 化学式: C₁₇H₂₂OS
• 分子量: 274.427
• InChiKey: GEEXJSPJRBPUOI-NTCAYCPXSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.35
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  香叶醇 、 一氧化碳 、 苯硫酚 在 palladium diacetate 、 对甲苯磺酸 、 三苯基膦 作用下， 以 二氯甲烷 为溶剂， 100.0 ℃ 、2.76 MPa 条件下， 反应 48.0h， 以84%的产率得到phenyl 4,8-dimethyl-3,7-nonadienethioate
  参考文献：
  名称：

  Highly Regioselective Thiocarbonylation of Allylic Alcohols with Thiols and Carbon Monoxide Catalyzed by Palladium Complexes:  A New and Efficient Route to β,γ-Unsaturated Thioesters

  摘要：

  The reaction of allylic alcohols with thiols and carbon monoxide in the presence of catalytic quantities of Pd(OAc)(2) (3 mol %), triphenylphosphine (12 mol %), and p-TsOH (5 mol %) leads to a novel thiocarbonylation to afford beta,gamma-unsaturated thioesters in good to excellent yields. Other palladium catalyst systems such as Pd-2(dba)(3). CHCl3-PPh3-p-TsOH, Pd(PPh3)(4)-p-TsOH, and Pd(OAc)(2)-dppb-p-TsOH are also effective for this transformation. The thiocarbonylation reaction is believed to proceed via a allylpalladium intermediate. The reaction occurs highly regioselectively at the least hindered allylic terminal carbon of the substrate to give the products. This new carbonylation procedure was readily applied to a variety of allylic alcohols and both aromatic and aliphatic thiols.

  DOI：

  10.1021/jo9812328

文献信息

• Highly Regioselective Thiocarbonylation of Conjugated Dienes via Palladium-Catalyzed Three-Component Coupling Reactions
  作者：Wen-Jing Xiao、Giuseppe Vasapollo、Howard Alper

  DOI：10.1021/jo000231o

  日期：2000.6.1

  Three-component coupling reaction of conjugated dienes, thiols, and carbon monoxide affords an atom-economical thiocarbonylation of the dienes to give beta,gamma-unsaturated thioesters as the sole products. A catalyst system based on [Pd(OAc)(2)] and Ph(3)P showed excellent catalytic activity. The thiocarbonylation was performed under an atmosphere of carbon monoxide (400 psi) at 110 degrees C in CH(2)Cl(2)

  共轭二烯，硫醇和一氧化碳的三组分偶联反应提供了二烯的原子经济的硫羰基化反应，从而以β，γ-不饱和硫代酯为唯一产物。基于[Pd（OAc）（2）]和Ph（3）P的催化剂体系显示出优异的催化活性。硫羰基化反应是在一氧化碳（400 psi）的气氛下，在CH（2）Cl（2）中于110摄氏度进行的，反应时间为60 h。从容易获得的起始原料合成了多种硫代酸酯，它们的产率高至优异。据信该反应通过eta（3）-烯丙基钯中间体进行。适用于多种共轭二烯的硫羰基化反应具有很高的区域选择性，后者取决于eta（3）-烯丙基铝配合物的空间特征和稳定性。
• Highly Regioselective Thiocarbonylation of Allylic Alcohols with Thiols and Carbon Monoxide Catalyzed by Palladium Complexes:  A New and Efficient Route to β,γ-Unsaturated Thioesters
  作者：Wen-Jing Xiao、Howard Alper

  DOI：10.1021/jo9812328

  日期：1998.10.1

  The reaction of allylic alcohols with thiols and carbon monoxide in the presence of catalytic quantities of Pd(OAc)(2) (3 mol %), triphenylphosphine (12 mol %), and p-TsOH (5 mol %) leads to a novel thiocarbonylation to afford beta,gamma-unsaturated thioesters in good to excellent yields. Other palladium catalyst systems such as Pd-2(dba)(3). CHCl3-PPh3-p-TsOH, Pd(PPh3)(4)-p-TsOH, and Pd(OAc)(2)-dppb-p-TsOH are also effective for this transformation. The thiocarbonylation reaction is believed to proceed via a allylpalladium intermediate. The reaction occurs highly regioselectively at the least hindered allylic terminal carbon of the substrate to give the products. This new carbonylation procedure was readily applied to a variety of allylic alcohols and both aromatic and aliphatic thiols.