(+/-)-1-[2H1]-Cyclopent-2-en-1-ol acetate | 219983-30-9

• 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: (+/-)-1-[2H1]-Cyclopent-2-en-1-ol acetate
• CAS: 219983-30-9
• 化学式: C₇H₁₀O₂
• 分子量: 127.147
• InChiKey: JMTLGVPTXJYPBX-WHRKIXHSSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.27
• 重原子数：
  9.0
• 可旋转键数：
  1.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  二甲基丙二酸钠 、 (+/-)-1-[2H1]-Cyclopent-2-en-1-ol acetate 在 bis(π-allylpalladium chloride) (1R,2R)-(+)-1,2-二氨基环己烷-N,N′-双(2-二苯基磷苯甲酰) 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 生成 dimethyl 2-(cyclopent-2-enyl)malonate 、 (1')[2H1]-Dimethyl (2'-cyclopentenyl)methanedicarboxylate 、 (3')[2H1]-Dimethyl (2'-cyclopentenyl)methanedicarboxylate
  参考文献：
  名称：

  Memory Effects in Pd-Catalysed Allylic Alkylation: Stereochemical Labelling through Isotopic Desymmetrization

  摘要：

  H-2-Labelled and O-18-labelled cyclopentenyl esters (+/-)-4 and (+/-)-5 are used as probes for memory effects in Pd-catalysed allylic alkylation. H-2-Labelled alkylation product 6 arising from stereospecific Pd-catalysed reaction of (+/-)-4 was analysed by a novel C-13 NMR method involving H-2-isotope shifts and paramagnetic diastereotopic shifts. When catalysts bearing the Trost modular ligand (R,R)-3 were employed, variable memory effects were observed with the slower reacting chirality mismatched (R)-4 substrate-catalyst pairing. The memory effect is dependent on nucleofuge steric bulk and not pK(a). Attack by [LiCH(CO2CH3)(2)] occurs with reversed site selectivity but (R)-4 remains the mismatched substrate. Mismatched ionisation leading to a Pd-pi-allyl in which (R,R)-3 acts as a monophosphine ligand may explain the memory effect.

  DOI：

  10.1002/(sici)1521-3765(19981204)4:12<2539::aid-chem2539>3.0.co;2-1
• 作为产物：
  描述：

  2-环戊烯酮 在 4-二甲氨基吡啶 、 lithium aluminium deuteride 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 24.0h， 生成 (+/-)-1-[2H1]-Cyclopent-2-en-1-ol acetate
  参考文献：
  名称：

  Memory Effects in Pd-Catalysed Allylic Alkylation: Stereochemical Labelling through Isotopic Desymmetrization

  摘要：

  H-2-Labelled and O-18-labelled cyclopentenyl esters (+/-)-4 and (+/-)-5 are used as probes for memory effects in Pd-catalysed allylic alkylation. H-2-Labelled alkylation product 6 arising from stereospecific Pd-catalysed reaction of (+/-)-4 was analysed by a novel C-13 NMR method involving H-2-isotope shifts and paramagnetic diastereotopic shifts. When catalysts bearing the Trost modular ligand (R,R)-3 were employed, variable memory effects were observed with the slower reacting chirality mismatched (R)-4 substrate-catalyst pairing. The memory effect is dependent on nucleofuge steric bulk and not pK(a). Attack by [LiCH(CO2CH3)(2)] occurs with reversed site selectivity but (R)-4 remains the mismatched substrate. Mismatched ionisation leading to a Pd-pi-allyl in which (R,R)-3 acts as a monophosphine ligand may explain the memory effect.

  DOI：

  10.1002/(sici)1521-3765(19981204)4:12<2539::aid-chem2539>3.0.co;2-1