1-({1-[Dimethyl-(2-methyl-allyl)-silanyl]-hexyloxy}-dimethyl-silanyl)-hexan-1-ol | 176038-03-2

• 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: 1-({1-[Dimethyl-(2-methyl-allyl)-silanyl]-hexyloxy}-dimethyl-silanyl)-hexan-1-ol
• 英文别名: 1-[1-[Dimethyl(2-methylprop-2-enyl)silyl]hexoxy-dimethylsilyl]hexan-1-ol
• CAS: 176038-03-2
• 化学式: C₂₀H₄₄O₂Si₂
• 分子量: 372.739
• InChiKey: HATZQSIJCAZQMP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  6.46
• 重原子数：
  24
• 可旋转键数：
  14
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.9
• 拓扑面积：
  29.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-({1-[Dimethyl-(2-methyl-allyl)-silanyl]-hexyloxy}-dimethyl-silanyl)-hexan-1-ol 在 三氟甲磺酸三甲基硅酯 作用下， 以 二氯甲烷 为溶剂， 生成 trimethyl[1-(1-pentylbut-3-enyloxy)hexyl]silane
  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-[二甲基(苯基)甲硅烷基]己烷-1-醇 在 吡啶 、 4-二甲氨基吡啶 、 四氟硼酸-二乙醚络合物 、 碘 、 magnesium 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 15.5h， 生成 1-({1-[Dimethyl-(2-methyl-allyl)-silanyl]-hexyloxy}-dimethyl-silanyl)-hexan-1-ol
  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

文献信息

• Highly Diastereoselective Intramolecular Allylation Reactions of Mixed Silyl-Substituted Acetals
  作者：Russell J. Linderman、Kangyi Chen

  DOI：10.1021/jo9517048

  日期：1996.1.1

  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.