1-[2H1]-Cyclopentenyl pivalate | 219983-22-9

• 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]-Cyclopentenyl pivalate
• 英文别名: (1-Deuteriocyclopent-2-en-1-yl) 2,2-dimethylpropanoate
• CAS: 219983-22-9
• 化学式: C₁₀H₁₆O₂
• 分子量: 169.228
• InChiKey: KISHVCOQZKTZHO-BNEYPBHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.7
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  二甲基丙二酸钠 、 1-[2H1]-Cyclopentenyl pivalate 在 [Pd(allyl)(MeCN)2][OTf] (1R,2R)-(+)-1,2-二氨基环己烷-N,N′-双(2-二苯基磷苯甲酰) 、 二苄叉丙酮 、 lithium chloride 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 以14%的产率得到(R)-(3')[2H1]-Dimethyl (2'-cyclopentenyl)methanedicarboxylate
  参考文献：
  名称：

  Chloride ion effects on kinetic resolution in Pd-catalysed allylic alkylation

  摘要：

  氯化物离子（5 mol%）加速并稳定环戊烯基特戊酸对托斯特模块化配体的Pd0复合物的反应，该反应属于反应较慢的对映异构体的氧化加成反应。

  DOI：

  10.1039/a806324i
• 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]-Cyclopentenyl pivalate
  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

文献信息

• Diastereoisomeric Cationic π-Allylpalladium-(P,C)-MAP and MOP Complexes and Their Relationship to Stereochemical Memory Effects in Allylic Alkylation
  作者：Guy C. Lloyd-Jones、Susanna C. Stephen、Martin Murray、Craig P. Butts、Ŝtěpán Vyskočil、Pavel Kočovský

  DOI：10.1002/1521-3765(20001201)6:23<4348::aid-chem4348>3.0.co;2-y

  日期：2000.12.1

  results in a more alkene-like character at the allyl terminus trans to phosphane ligand. The opposite allyl terminus, which is trans to the ipsocarbon atom (C1'), is more strongly bound and the dominant allyl stereodynamic process involves C-C bond rotation in an n'-allyl intermediate bound through this carbon. Palladium complexes of MAP and MOP are very efficient catalysts for allylic alkylation of racemic

  轴向手性配体2-（二苯基膦基）-2'-甲氧基-1,1'-联萘（MOP; 6）和2'-二甲基氨基-2-（二苯基膦基）-1,1'-联萘（MAP; 7）配位通过三芳基膦和ipso-碳原子（C1'）以不寻常的双齿（P，C）模式连接到阳离子烯丙基钯片段。易于制备的MAP和MOP配合物[Pd [（P，C）-（L）] [n3-烯丙基]] [OTf]（9（L = 7）和10（L = 6））已在溶液中进行了表征（ NMR），其中观察到两个非对映异构的旋转异构体。旋转异构体的立体化学特征是通过一维和二维NMR光谱实验确定的。在固态和溶液中，烯丙基单元均显示为以略微扭曲的n3-模式进行配位，从而导致烯丙基末端反式转变为膦配体时具有更像烯烃的特征。相对的烯丙基末端更紧密地键合，该烯丙基末端与ipsocarbon原子（C1'）相连，而主要的烯丙基立体动力学过程涉及通过该碳键合的n'-烯丙基中间体中的CC键旋转。MA
• Memory Effects in Pd-Catalysed Allylic Alkylation: Stereochemical Labelling through Isotopic Desymmetrization
  作者：Guy C. Lloyd-Jones、Susanna C. Stephen

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

  日期：1998.12.4

  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.
• Chloride ion effects on kinetic resolution in Pd-catalysed allylic alkylation
  作者：Guy C. Lloyd-Jones、Susanna C. Stephen

  DOI：10.1039/a806324i

  日期：——

  Chloride ion (5 mol%) accelerates and stabilises the oxidative addition of the slow-reacting enantiomer of cyclopentenyl pivaloate to Pd0 complexes bearing the Trost modular ligand.

  氯化物离子（5 mol%）加速并稳定环戊烯基特戊酸对托斯特模块化配体的Pd0复合物的反应，该反应属于反应较慢的对映异构体的氧化加成反应。