[1-(cyclohex-1-enyl)cyclobutoxy]trimethylsilane | 757249-52-8

• 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-(cyclohex-1-enyl)cyclobutoxy]trimethylsilane
• 英文别名: [1-(Cyclohexen-1-yl)cyclobutyl]oxy-trimethylsilane
• CAS: 757249-52-8
• 化学式: C₁₃H₂₄OSi
• 分子量: 224.418
• InChiKey: BJXOVHPLMIIGMW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.26
• 重原子数：
  15
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.85
• 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：

  [1-(cyclohex-1-enyl)cyclobutoxy]trimethylsilane 在 四氯化钛 间氯过氧苯甲酸 作用下， 以 二氯甲烷 为溶剂， 反应 18.5h， 生成 (5SR,6SR)-6-hydroxyspiro[4.5]decan-1-one
  参考文献：
  名称：

  Investigations of α-Siloxy−Epoxide Ring Expansions Forming 1-Azaspirocyclic Ketones

  摘要：

  The construction of 1-azaspirocyclic cycloalkanones using a siloxy-epoxide semipinacol ring expansion process was examined. Functionalized 1-azaspiro[5.5]undecan-7-ones (1-azaspirocyclic cyclohexanones) proceeded in high chemical yields with complete diastereoselectivity using titanium tetrachloride as the Lewis acid promoter. The formation of functionalized 6-azaspiro[5.4]-decan-1-ones (1-azaspirocyclic cyclopentanones) proceeded in high chemical yield with little diastereoselectivity. Modification of reaction parameters such as the Lewis acid promoter or the nature of the silyl ether allowed for the preferential formation of either ("anti" or "syn" 1,2 alkyl shift) diastereomeric product. An explanation for the different reactivity profiles between the cyclobutanol silyl ethers and cyclopentanol silyl ethers is provided.

  DOI：

  10.1021/jo049356+
• 作为产物：
  描述：

  1-氯环己烯 在 2,6-二甲基吡啶 、 lithium 作用下， 以 四氢呋喃 、 乙醚 为溶剂， 反应 15.0h， 生成 [1-(cyclohex-1-enyl)cyclobutoxy]trimethylsilane
  参考文献：
  名称：

  Investigations of α-Siloxy−Epoxide Ring Expansions Forming 1-Azaspirocyclic Ketones

  摘要：

  The construction of 1-azaspirocyclic cycloalkanones using a siloxy-epoxide semipinacol ring expansion process was examined. Functionalized 1-azaspiro[5.5]undecan-7-ones (1-azaspirocyclic cyclohexanones) proceeded in high chemical yields with complete diastereoselectivity using titanium tetrachloride as the Lewis acid promoter. The formation of functionalized 6-azaspiro[5.4]-decan-1-ones (1-azaspirocyclic cyclopentanones) proceeded in high chemical yield with little diastereoselectivity. Modification of reaction parameters such as the Lewis acid promoter or the nature of the silyl ether allowed for the preferential formation of either ("anti" or "syn" 1,2 alkyl shift) diastereomeric product. An explanation for the different reactivity profiles between the cyclobutanol silyl ethers and cyclopentanol silyl ethers is provided.

  DOI：

  10.1021/jo049356+

文献信息

• A Mn(<scp>iii</scp>)/TEMPO-co-mediated tandem azidation–1,2-carbon migration reaction of allylic silyl ethers
  作者：Zhi-Min Chen、Zhen Zhang、Yong-Qiang Tu、Ming-Hui Xu、Fu-Min Zhang、Chen-Chen Li、Shao-Hua Wang

  DOI：10.1039/c4cc04707a

  日期：——

  A novel Mn(III)/TEMPO-co-mediated tandem azidation-1,2-carbon migration reaction of allylic silyl ethers with an unactivated C=C bond has been explored, generating alpha-aryl-alkyl beta-azido ketones with an alpha-quaternary stereocenter.

  探索了一种新型的Mn（III）/ TEMPO-co介导的具有未活化C = C键的烯丙基甲硅烷基醚串联叠氮化-1,2-碳迁移反应，产生了具有α -四元立体中心。
• Investigations of α-Siloxy−Epoxide Ring Expansions Forming 1-Azaspirocyclic Ketones
  作者：Gregory R. Dake、Michaël D. B. Fenster、Mélissa Fleury、Brian O. Patrick

  DOI：10.1021/jo049356+

  日期：2004.8.1

  The construction of 1-azaspirocyclic cycloalkanones using a siloxy-epoxide semipinacol ring expansion process was examined. Functionalized 1-azaspiro[5.5]undecan-7-ones (1-azaspirocyclic cyclohexanones) proceeded in high chemical yields with complete diastereoselectivity using titanium tetrachloride as the Lewis acid promoter. The formation of functionalized 6-azaspiro[5.4]-decan-1-ones (1-azaspirocyclic cyclopentanones) proceeded in high chemical yield with little diastereoselectivity. Modification of reaction parameters such as the Lewis acid promoter or the nature of the silyl ether allowed for the preferential formation of either ("anti" or "syn" 1,2 alkyl shift) diastereomeric product. An explanation for the different reactivity profiles between the cyclobutanol silyl ethers and cyclopentanol silyl ethers is provided.