[3-(Bromomethyl)-2-phenylbut-3-enoxy]-tert-butyl-dimethylsilane | 204335-10-4

• 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: [3-(Bromomethyl)-2-phenylbut-3-enoxy]-tert-butyl-dimethylsilane
• CAS: 204335-10-4
• 化学式: C₁₇H₂₇BrOSi
• 分子量: 355.39
• InChiKey: SVPRNLDUALSXHO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.74
• 重原子数：
  20
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.53
• 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：

  [3-(Bromomethyl)-2-phenylbut-3-enoxy]-tert-butyl-dimethylsilane 在 indium 、 对甲苯磺酸 作用下， 以 甲醇 、 水 为溶剂， 生成 (1S,4R)-3-methylidene-1,4-diphenylpentane-1,5-diol
  参考文献：
  名称：

  Effective 1,4-Asymmetric C−C/C−O Stereoinduction in Indium-Promoted Coupling Reactions of Aldehydes to Protected and Unprotected [1-(Bromomethyl)vinyl] Alkanols. The Status of Intramolecular Chelation within Functionalized Allylindium Reagents

  摘要：

  The stereochemistry of the coupling reactions of oxygen-substituted bromides 8-10 with isobutyraldehyde, benzaldehyde, and cyclohexanecarboxaldehyde in water is described. The examples involving the O-silylated derivatives 8 exhibit moderate anti stereoselectivity. In contrast, rather high (most often in excess of 80:20) syn diastereofacial bias is observed when hydroxy bromides 10 are involved. Consequently, stereocontrolled 1,4-asymmetric induction under aqueous conditions can be realized in either direction on demand. These results are considered to reflect the fact that the siloxy systems enter into C-C bond formation via conventional Felkin-Anh transition state arrangements. The crossover observed for the unprotected analogues is believed to be a consequence of the preferred adoption of chelated transition states, these interactions likely being fundamental to aqueous organometallic chemistry.

  DOI：

  10.1021/jo9715534
• 作为产物：
  描述：

  (Z)-methyl 2-(bromomethyl)-3-phenylacrylate 在 咪唑 、 indium 、 N-溴代丁二酰亚胺(NBS) 、 二异丁基氢化铝 、 三苯基膦 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 、 水 为溶剂， 反应 42.0h， 生成 [3-(Bromomethyl)-2-phenylbut-3-enoxy]-tert-butyl-dimethylsilane
  参考文献：
  名称：

  Effective 1,4-Asymmetric C−C/C−O Stereoinduction in Indium-Promoted Coupling Reactions of Aldehydes to Protected and Unprotected [1-(Bromomethyl)vinyl] Alkanols. The Status of Intramolecular Chelation within Functionalized Allylindium Reagents

  摘要：

  The stereochemistry of the coupling reactions of oxygen-substituted bromides 8-10 with isobutyraldehyde, benzaldehyde, and cyclohexanecarboxaldehyde in water is described. The examples involving the O-silylated derivatives 8 exhibit moderate anti stereoselectivity. In contrast, rather high (most often in excess of 80:20) syn diastereofacial bias is observed when hydroxy bromides 10 are involved. Consequently, stereocontrolled 1,4-asymmetric induction under aqueous conditions can be realized in either direction on demand. These results are considered to reflect the fact that the siloxy systems enter into C-C bond formation via conventional Felkin-Anh transition state arrangements. The crossover observed for the unprotected analogues is believed to be a consequence of the preferred adoption of chelated transition states, these interactions likely being fundamental to aqueous organometallic chemistry.

  DOI：

  10.1021/jo9715534

文献信息

• Competitive Intramolecular/Intermolecular Chelation Options Operative during Indium-Promoted Additions to Pyridyl Aldehydes and to Glyoxylic Acid under Aqueous Conditions
  作者：Leo A. Paquette、Roger R. Rothhaar

  DOI：10.1021/jo981717w

  日期：1999.1.1

  The stereochemical course of the 1,2-addition of six allylindium reagents to 2- and 3-pyridinecarboxaldehyde and to glyoxylic acid has been investigated in order to assess the level and direction of diastereoselectivity in these coupling reactions. When 2-PyCHO is involved, the results strongly suggest that the ring nitrogen becomes chelated to the indium atom in the aqueous environment. One striking observation is the crossover in stereoselectivity seen relative to the use of 3-PyCHO. A second revealing fact is the significantly faster rate of reaction of 2-PyCHO, as long as steric effects are not allowed to interfere. The varying product distributions observed in the latter experiments are attributed to other control elements such as intramolecular chelation within the indium reagent and nonbonded steric restrictions resident in either or both reaction partners. In the absence of extramolecular chelating events (e.g., when 3-PyCHO is involved), adherence to Felkin-Anh transition-state alignments is presumably exercised. The previous working assumption that indium(III) is capable of chelation to flanking heteroatomic centers in water is supported by the present investigation.