[3-(Bromomethyl)-2-propan-2-ylbut-3-enoxy]-tert-butyl-dimethylsilane | 204335-09-1

• 分子结构分类: 有机化合物 - 有机金属化合物 - 有机类金属化合物
• 英文名称: [3-(Bromomethyl)-2-propan-2-ylbut-3-enoxy]-tert-butyl-dimethylsilane
• CAS: 204335-09-1
• 化学式: C₁₄H₂₉BrOSi
• 分子量: 321.373
• InChiKey: IRHIEWNWTRWUPR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.23
• 重原子数：
  17
• 可旋转键数：
  7
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 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-propan-2-ylbut-3-enoxy]-tert-butyl-dimethylsilane 在 indium 、 对甲苯磺酸 作用下， 以 甲醇 、 水 为溶剂， 生成
  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：

  methyl 3-(hydroxymethyl)-4-methyl-2-methylenepentanoate 在 咪唑 、 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 为溶剂， 反应 22.0h， 生成 [3-(Bromomethyl)-2-propan-2-ylbut-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

• Paquette, Leo A., Synthesis, 2003, # 5, p. 765 - 774
  作者：Paquette, Leo A.

  DOI：——

  日期：——