ethyl 3-(2-methyl-1-((trimethylsilyl)methyl)-1-propenyl)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: ethyl 3-(2-methyl-1-((trimethylsilyl)methyl)-1-propenyl)benzoate
• 英文别名: Ethyl 3-(3-methyl-1-trimethylsilylbut-2-en-2-yl)benzoate
• 化学式: C₁₇H₂₆O₂Si
• 分子量: 290.478
• InChiKey: YDOZAOOVQSYVLX-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.99
• 重原子数：
  20
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  3-甲基-1,2-丁二烯 、 3-碘苯甲酸乙酯 、 叔丁基锡烷 在 bis(dibenzylideneacetone)-palladium⁽⁰⁾ 作用下， 以 甲苯 为溶剂， 反应 7.0h， 以82%的产率得到ethyl 3-(2-methyl-1-((trimethylsilyl)methyl)-1-propenyl)benzoate
  参考文献：
  名称：

  Carbosilylation of Allenes Catalyzed by Palladium Complexes:  A New Efficient Route to Substituted Allylic Silanes

  摘要：

  An aromatic or olefinic halide RX (C6H5I, p-CH3COC6H4I, p-NO2C6H4I, p-CH3OC6H4I, o-CH3OC6H4I, m-C2H5OCOC6H4I, (Z)-C2H5OCOCH=CHI, 3-iodocyclopent-2-en-1-one, 1-iodothiophene, 1-iodonaphthalene, 3-bromo-5,5-dimethylcyclohex-2-en-1-one, or alpha-bromostyrene), Bu3SnSiMe3 (2), and 1,1-dimethylallene (3a) undergo three-component coupling reaction in toluene in the presence of Pd(dba)(2) (dba = dibenzylideneacetone) to give an allylic silane (Me)(2)C=C(R)CH2SiMe3 in good to excellent yields. When X = I, the yields are substantially higher than when X = Br or Cl (no reaction). This carbosilylation reaction is highly regioselective, with the R group adding to the middle carbon and the silyl group to the unsubstituted terminal carbon of 3a. Monosubstituted allenes R " CH=C=CH2 (R " = cyclo-C6H11, n-Bu, and Ph) also undergo carbosilylation with PhI and 2, producing R " CH=C(Ph)CH2SiMe3 stereoselectively with Z/E between 98/2 and 80/20. Bulkier organic halides and allenes give products with higher Z/E ratios. Based on known palladium-allene and -allyl chemistry, we propose a mechanism to account for this palladium-catalyzed three-component coupling reaction.

  DOI：

  10.1021/jo982307a

文献信息

• Carbosilylation of Allenes Catalyzed by Palladium Complexes:  A New Efficient Route to Substituted Allylic Silanes
  作者：Ming-Yuan Wu、Feng-Yu Yang、Chien-Hong Cheng

  DOI：10.1021/jo982307a

  日期：1999.4.1

  An aromatic or olefinic halide RX (C6H5I, p-CH3COC6H4I, p-NO2C6H4I, p-CH3OC6H4I, o-CH3OC6H4I, m-C2H5OCOC6H4I, (Z)-C2H5OCOCH=CHI, 3-iodocyclopent-2-en-1-one, 1-iodothiophene, 1-iodonaphthalene, 3-bromo-5,5-dimethylcyclohex-2-en-1-one, or alpha-bromostyrene), Bu3SnSiMe3 (2), and 1,1-dimethylallene (3a) undergo three-component coupling reaction in toluene in the presence of Pd(dba)(2) (dba = dibenzylideneacetone) to give an allylic silane (Me)(2)C=C(R)CH2SiMe3 in good to excellent yields. When X = I, the yields are substantially higher than when X = Br or Cl (no reaction). This carbosilylation reaction is highly regioselective, with the R group adding to the middle carbon and the silyl group to the unsubstituted terminal carbon of 3a. Monosubstituted allenes R " CH=C=CH2 (R " = cyclo-C6H11, n-Bu, and Ph) also undergo carbosilylation with PhI and 2, producing R " CH=C(Ph)CH2SiMe3 stereoselectively with Z/E between 98/2 and 80/20. Bulkier organic halides and allenes give products with higher Z/E ratios. Based on known palladium-allene and -allyl chemistry, we propose a mechanism to account for this palladium-catalyzed three-component coupling reaction.