(+)-(3S)-3-(tert-butyldimethylsilyloxy)-1-(toluene-4-sulfonyl)-6-(1-triisopropylsilyloxycyclobutyl)-1,2,3,4-tetrahydropyridine | 757249-50-6

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (+)-(3S)-3-(tert-butyldimethylsilyloxy)-1-(toluene-4-sulfonyl)-6-(1-triisopropylsilyloxycyclobutyl)-1,2,3,4-tetrahydropyridine
• 英文别名: tert-butyl-dimethyl-[[(3S)-1-(4-methylphenyl)sulfonyl-6-[1-tri(propan-2-yl)silyloxycyclobutyl]-3,4-dihydro-2H-pyridin-3-yl]oxy]silane
• CAS: 757249-50-6
• 化学式: C₃₁H₅₅NO₄SSi₂
• 分子量: 594.019
• InChiKey: BAXXCJSIRZZMQX-MHZLTWQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  8.78
• 重原子数：
  39
• 可旋转键数：
  11
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.74
• 拓扑面积：
  64.2
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (+)-(3S)-3-(tert-butyldimethylsilyloxy)-1-(toluene-4-sulfonyl)-6-(1-triisopropylsilyloxycyclobutyl)-1,2,3,4-tetrahydropyridine 在 四氯化钛 二甲基二环氧乙烷 、 potassium carbonate 作用下， 以 二氯甲烷 、 丙酮 为溶剂， 反应 0.5h， 生成 (+)-(5S,8S,10S)-8-(tert-butyldimethylsilyloxy)-10-hydroxy-6-(toluene-4-sulfonyl)-6-azaspiro[5.4]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：

  三异丙基硅基三氟甲磺酸酯 、 (+)-(5S)-1-[5-(tert-butyldimethylsilyloxy)-1-(toluene-4-sulfonyl)-1,4,5,6-tetrahydropyridin-2-yl]-cyclobutanol 在 2,6-二甲基吡啶 作用下， 以 四氢呋喃 为溶剂， 以94%的产率得到(+)-(3S)-3-(tert-butyldimethylsilyloxy)-1-(toluene-4-sulfonyl)-6-(1-triisopropylsilyloxycyclobutyl)-1,2,3,4-tetrahydropyridine
  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

• 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.