1-((trimethylsilyl)oxy)-1-methoxy-1,3-hexadiene | 131489-41-3

• 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-((trimethylsilyl)oxy)-1-methoxy-1,3-hexadiene
• 英文别名: 1-<(trimethylsilyl)oxy>-1-methoxy-1,3-hexadiene；1-trimethylsilyloxy-1-methoxy-1,3(E)-hexadiene；1-[(trimethylsilyl)oxy]-1-methoxy-1,3-hexadiene
• CAS: 131489-41-3；131489-42-4
• 化学式: C₁₀H₂₀O₂Si
• 分子量: 200.353
• InChiKey: AVGRNKIMMWJWJE-JSGCFVPUSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.29
• 重原子数：
  13.0
• 可旋转键数：
  5.0
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.6
• 拓扑面积：
  18.46
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  1-((trimethylsilyl)oxy)-1-methoxy-1,3-hexadiene 在 zinc(II) chloride 作用下， 以 二氯甲烷 、 乙酸乙酯 为溶剂， 生成 methyl (E)-4-(benzylamino)hex-2-enoate
  参考文献：
  名称：

  Regiochemical control in the preparation of 2-(nosyloxy) .beta.,.gamma.-unsaturated esters and 4-(nosyloxy) .alpha.,.beta.-unsaturated esters from 1-[(trimethylsilyl)oxy]-1-alkoxy 1,3-dienes

  摘要：

  A series of 1-[(trialkylsilyl)oxy]-1-alkoxy 1,3-dienes 1a-i were found to react with p-nitrobenzenesulfonyl peroxide in the presence of sodium methoxide or zinc chloride to give alkyl 2-[[(p-nitrophenyl)sulfonyl]oxy] beta-gamma-unsaturated esters 3 and alkyl 4-[[(p-nitrophenyl)sulfonyl]oxy] alpha,beta-unsaturated esters 4 which are readily separable. The regioselectivity is determined by kinetic versus thermodynamic control. When positions 2 or 4 of the diene are unsubstituted, the 2-isomer is the major product and is the kinetically fastest formed product. It can be thermally rearranged to the more stable 4-isomer. When alkyl substituents are present at either the 2- or 4-positions, only the 4-isomer is obtained. Substitution for nosylate by amine nucleophiles occurs by an S(N)2 process. Thus 2-amino beta,gamma-unsaturated esters and 4-amino alpha,beta-unsaturated esters can be prepared from the appropriate starting nosylate.

  DOI：

  10.1021/jo00003a022
• 作为产物：
  描述：

  三甲基氯硅烷 、 反式-2-己烯甲酯 在 六甲基磷酰三胺 、 lithium diisopropyl amide 作用下， 生成 1-((trimethylsilyl)oxy)-1-methoxy-1,3-hexadiene
  参考文献：
  名称：

  Regiochemical control in the preparation of 2-(nosyloxy) .beta.,.gamma.-unsaturated esters and 4-(nosyloxy) .alpha.,.beta.-unsaturated esters from 1-[(trimethylsilyl)oxy]-1-alkoxy 1,3-dienes

  摘要：

  A series of 1-[(trialkylsilyl)oxy]-1-alkoxy 1,3-dienes 1a-i were found to react with p-nitrobenzenesulfonyl peroxide in the presence of sodium methoxide or zinc chloride to give alkyl 2-[[(p-nitrophenyl)sulfonyl]oxy] beta-gamma-unsaturated esters 3 and alkyl 4-[[(p-nitrophenyl)sulfonyl]oxy] alpha,beta-unsaturated esters 4 which are readily separable. The regioselectivity is determined by kinetic versus thermodynamic control. When positions 2 or 4 of the diene are unsubstituted, the 2-isomer is the major product and is the kinetically fastest formed product. It can be thermally rearranged to the more stable 4-isomer. When alkyl substituents are present at either the 2- or 4-positions, only the 4-isomer is obtained. Substitution for nosylate by amine nucleophiles occurs by an S(N)2 process. Thus 2-amino beta,gamma-unsaturated esters and 4-amino alpha,beta-unsaturated esters can be prepared from the appropriate starting nosylate.

  DOI：

  10.1021/jo00003a022

文献信息

• Regioselective addition of 1-trimethylsilyloxy-1-methoxy-1,3-dienes to aldonitrones catalysed by trimethylsilyl triflate
  作者：Chiara Camiletti、Dilip D. Dhavale、Franco Donati、Claudio Trombini

  DOI：10.1016/0040-4039(95)01468-w

  日期：1995.10

  1-Trimethylsilyloxy-1-methoxy-1,3-dienes (3a-d) regioselectively add to aldonitrones at -20 degrees C in dichloromethane in the presence of 10-20 % of trimethylsilyl triflate to give gamma-adducts in high yields; on the other hand, 1-trimethylsilyloxy-1-methoxy-1,3-hexadiene (3e) displayes a reversed regiochemical preference affording the alpha-adduct as the major product.