methoxyethyl 1-(dimethylmethoxysilyl)-2-methylpropyl ether | 176038-29-2

• 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: methoxyethyl 1-(dimethylmethoxysilyl)-2-methylpropyl ether
• 英文别名: Methoxy-[1-(1-methoxyethoxy)-2-methylpropyl]-dimethylsilane
• CAS: 176038-29-2
• 化学式: C₁₀H₂₄O₃Si
• 分子量: 220.384
• InChiKey: CWYCGKYQLNGRTF-UHFFFAOYSA-N

物化性质

• 沸点：
  200.3±20.0 °C(Predicted)
• 密度：
  0.883±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.41
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  27.7
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  methoxyethyl 1-(dimethylmethoxysilyl)-2-methylpropyl ether 在 氢氧化钾 、 正丁基锂 、 三氟甲磺酸三甲基硅酯 作用下， 反应 2.33h， 生成
  参考文献：
  名称：

  Highly Diastereoselective Intramolecular Allylation Reactions of Mixed Silyl-Substituted Acetals

  摘要：

  The reaction of preformed mixed acetals derived from (alpha-hydroxyalkyl)dimethylallylsilane with a number of aromatic and aliphatic aldehydes in the presence of Lewis acids results in a highly diastereoselective intramolecular allylation reaction. The reaction proceeds through a cyclic synclinal S-E' addition of the allylsilane to an intermediate oxocarbenium ion. The reaction occurs exclusively by an intramolecular process as determined by means of a cross-over experiment. The relative stereochemistry was determined by the conversion of one of the allylation products to a known (stereodefined) aldol-type product. A greater degree of diastereoselectivity is obtained by in-situ formation of an oxocarbenium ion from (alpha-hydroxyhexyl)dimethylallylsilane and an aldehyde in the presence of boron trifluoride etherate. The diastereoselectivity of the in-situ allylation reaction typically exceeds 100:1 in favor of the syn adduct. However, reactions with electron rich aryl aldehydes resulted in a diminished degree of diastereoselectivity. The initial product of the in-situ reaction is an unstable silyl fluoride which is readily hydrolyzed to a silanol derivative upon reaction with methanolic potassium hydroxide. The overall yield of the two-step process is greater than 80%. A method for the synthesis of more highly substituted (alpha-alkoxyalkyl)dimethylallylsilanes by allyl anion displacement of methoxide from silicon is also described. The methyl siloxane derivatives were obtained by ozonolytic cleavage of an unsubstituted allyl group in methanol.

  DOI：

  10.1021/jo9517048
• 作为产物：
  描述：

  1--2-methylpropan-1-ol 在 4-二甲氨基吡啶 、 二甲基硫 、 臭氧 、 N,N-二异丙基乙胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 生成 methoxyethyl 1-(dimethylmethoxysilyl)-2-methylpropyl ether
  参考文献：
  名称：

  Highly Diastereoselective Intramolecular Allylation Reactions of Mixed Silyl-Substituted Acetals

  摘要：

  The reaction of preformed mixed acetals derived from (alpha-hydroxyalkyl)dimethylallylsilane with a number of aromatic and aliphatic aldehydes in the presence of Lewis acids results in a highly diastereoselective intramolecular allylation reaction. The reaction proceeds through a cyclic synclinal S-E' addition of the allylsilane to an intermediate oxocarbenium ion. The reaction occurs exclusively by an intramolecular process as determined by means of a cross-over experiment. The relative stereochemistry was determined by the conversion of one of the allylation products to a known (stereodefined) aldol-type product. A greater degree of diastereoselectivity is obtained by in-situ formation of an oxocarbenium ion from (alpha-hydroxyhexyl)dimethylallylsilane and an aldehyde in the presence of boron trifluoride etherate. The diastereoselectivity of the in-situ allylation reaction typically exceeds 100:1 in favor of the syn adduct. However, reactions with electron rich aryl aldehydes resulted in a diminished degree of diastereoselectivity. The initial product of the in-situ reaction is an unstable silyl fluoride which is readily hydrolyzed to a silanol derivative upon reaction with methanolic potassium hydroxide. The overall yield of the two-step process is greater than 80%. A method for the synthesis of more highly substituted (alpha-alkoxyalkyl)dimethylallylsilanes by allyl anion displacement of methoxide from silicon is also described. The methyl siloxane derivatives were obtained by ozonolytic cleavage of an unsubstituted allyl group in methanol.

  DOI：

  10.1021/jo9517048