methyl (1R,4S)-3-diethoxyphosphoryloxy-4,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxylate | 135616-09-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 有机磷酸及其衍生物
• 英文名称: methyl (1R,4S)-3-diethoxyphosphoryloxy-4,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxylate
• CAS: 135616-09-0
• 化学式: C₁₆H₂₇O₆P
• 分子量: 346.361
• InChiKey: KLRJIRHCALLJQF-MEDUHNTESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.07
• 重原子数：
  23.0
• 可旋转键数：
  7.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  71.06
• 氢给体数：
  0.0
• 氢受体数：
  6.0

反应信息

• 作为反应物：
  描述：

  methyl (1R,4S)-3-diethoxyphosphoryloxy-4,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxylate 在 吡啶 、 4-二甲氨基吡啶 、 偶氮二异丁腈 、 三氯溴甲烷 作用下， 以 乙醚 为溶剂， 反应 3.0h， 生成 3-bromo-born-2-ene
  参考文献：
  名称：

  Regioselective conversion of cycloalkanones to vinyl bromides with 1,2-functionality transposition. A general stratagem

  摘要：

  Cyclic beta-keto esters, available by regioselective acylation of cycloalkanone enolates, are rapidly transformed to alpha,beta-unsaturated acids. This functionality transposition allows the derived 3-hydroxy-4-methylthiazole-2-(3H)-thione derivatives to serve as precursors to synthetically useful vinyl bromides. The process involves heating the hydroxamate ester with AIBN in bromotrichloromethane solution. Alkylative and ring contractive variants of the methodology are highlighted. The short sequence makes available precursors to vinyl anions that are not otherwise conveniently accessible.

  DOI：

  10.1021/jo00021a044
• 作为产物：
  描述：

  白樟油 在 sodium hydride 作用下， 以 四氢呋喃 为溶剂， 生成 methyl (1R,4S)-3-diethoxyphosphoryloxy-4,7,7-trimethylbicyclo[2.2.1]hept-2-ene-2-carboxylate
  参考文献：
  名称：

  Regioselective conversion of cycloalkanones to vinyl bromides with 1,2-functionality transposition. A general stratagem

  摘要：

  Cyclic beta-keto esters, available by regioselective acylation of cycloalkanone enolates, are rapidly transformed to alpha,beta-unsaturated acids. This functionality transposition allows the derived 3-hydroxy-4-methylthiazole-2-(3H)-thione derivatives to serve as precursors to synthetically useful vinyl bromides. The process involves heating the hydroxamate ester with AIBN in bromotrichloromethane solution. Alkylative and ring contractive variants of the methodology are highlighted. The short sequence makes available precursors to vinyl anions that are not otherwise conveniently accessible.

  DOI：

  10.1021/jo00021a044

文献信息

• Regioselective conversion of cycloalkanones to vinyl bromides with 1,2-functionality transposition. A general stratagem
  作者：Leo A. Paquette、Karl Dahnke、Julien Doyon、Wei He、Kenetha Wyant、Dirk Friedrich

  DOI：10.1021/jo00021a044

  日期：1991.10

  Cyclic beta-keto esters, available by regioselective acylation of cycloalkanone enolates, are rapidly transformed to alpha,beta-unsaturated acids. This functionality transposition allows the derived 3-hydroxy-4-methylthiazole-2-(3H)-thione derivatives to serve as precursors to synthetically useful vinyl bromides. The process involves heating the hydroxamate ester with AIBN in bromotrichloromethane solution. Alkylative and ring contractive variants of the methodology are highlighted. The short sequence makes available precursors to vinyl anions that are not otherwise conveniently accessible.