cis-diethyl 5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: cis-diethyl 5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate
• 英文别名: (Z)-5-methoxycarbonyl-2-cyclohexenyl diethyl phosphate；(Z)-5-(methoxycarbonyl)-2-cyclohexen-1-yl diethyl phosphate；methyl (1S,5S)-5-[diethoxy(oxido)phosphaniumyl]oxycyclohex-3-ene-1-carboxylate
• 化学式: C₁₂H₂₁O₆P
• 分子量: 292.269
• InChiKey: QOAQLUKFQITORV-WDEREUQCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.2
• 重原子数：
  19
• 可旋转键数：
  8
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  77
• 氢给体数：
  0
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  cis-diethyl 5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate 在 sodium azide 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 (E)-methyl 5-azido-3-cyclohexenecarboxylate
  参考文献：
  名称：

  Palladium(0)-catalyzed azidation of allyl esters. Selective synthesis of allyl azides, primary allylamines, and related compounds

  摘要：

  DOI：

  10.1021/jo00275a011
• 作为产物：
  描述：

  cis-methyl 5-hydroxycyclohex-3-enecarboxylate 、 氯磷酸二乙酯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 0.5h， 以100%的产率得到cis-diethyl 5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate
  参考文献：
  名称：

  Palladium(0)-catalyzed azidation of allyl esters. Selective synthesis of allyl azides, primary allylamines, and related compounds

  摘要：

  DOI：

  10.1021/jo00275a011

文献信息

• Palladium(0)-catalyzed carbonylation of allyl phosphates and allyl acetates. Selective synthesis of β,γ-unsaturated esters
  作者：Shun-Ichi Murahashi、Yasushi Imada、Yuki Taniguchi、Shin-ya Higashiura

  DOI：10.1016/s0040-4039(00)80648-6

  日期：1988.1

  Palladium catalyzed carbonylations of allyl phosphates and allyl acetates give β,γ-unsaturated esters efficiently. The latter reaction requires bromide ion as a co-catalyst.

  钯催化的烯丙基磷酸酯和乙酸烯丙酯的羰基化反应可有效地生成β，γ-不饱和酯。后一反应需要溴离子作为助催化剂。
• Palladium(o)-catalyzed hydroxylamination of allyl esters
  作者：Shun-Ichi Murahashi∗、Yasushi Imada、Yuki Taniguchi、Yoichi Kodera

  DOI：10.1016/0040-4039(88)85061-5

  日期：1988.1

  Palladium-catalyzed reaction of allyl esters with hydroxylamines gives N-allylhydroxylamines, which are readily converted into secondary allylamines upon treatment with zinc powder in a dilute HCl solution.

  烯丙基酯与羟胺的钯催化反应生成N-烯丙基羟胺，在稀HCl溶液中用锌粉处理后，N-烯丙基羟胺很容易转化为仲烯丙胺。
• Palladium(0)-catalyzed alkoxycarbonylation of allyl phosphates and acetates
  作者：Shunichi Murahashi、Yasushi Imada、Yuki Taniguchi、Shinya Higashiura

  DOI：10.1021/jo00058a040

  日期：1993.3

  Palladium-catalyzed alkoxycarbonylation of allyl phosphates under CO (1 atm) at 50-degrees-C proceeds highly efficiently to give the corresponding beta,gamma-unsaturated esters. The carbonylation of geranyl phosphate ((E)-11) under CO (1 atm) at 50-degrees-C gave ethyl ester of homogeranic acid ((E)-12) stereoselectively. The carbonylation takes place at the least substituted allylic positions with inversion of configuration. Typically, the methoxycarbonylation of cis-5-(methoxycarbonyl)-2-cyclohexen-1-yl phosphate (cis-16) gave trans-dimethyl 2-cyclohexene-1,5-dicarboxylate (trans-17) selectively. Alkoxycarbonylation of allyl acetates is performed for the first time in the presence of a catalytic amount of bromide ion. The reaction can be rationalized by assuming the mechanism which involves oxidative addition of palladium(0) species to allyl acetates to give pi-allylpalladium acetate, fast ligand exchange of the acetate with bromide, insertion of carbon monoxide to give acylpalladium species, and alkoxylation.
• Palladium(0)-catalyzed azidation of allyl esters. Selective synthesis of allyl azides, primary allylamines, and related compounds
  作者：Shunichi Murahashi、Yuki Taniguchi、Yasushi Imada、Yoshio Tanigawa

  DOI：10.1021/jo00275a011

  日期：1989.7