(+/-)-1-[2H1]-Cyclopent-2-en-1-ol methyl carbonate | 220112-73-2

• 英文名称: (+/-)-1-[2H1]-Cyclopent-2-en-1-ol methyl carbonate
• CAS: 220112-73-2
• 化学式: C₇H₁₀O₃
• 分子量: 143.147
• InChiKey: YCYQMWIECYIIKT-RAMDWTOOSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.49
• 重原子数：
  10.0
• 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：
  35.53
• 氢给体数：
  0.0
• 氢受体数：
  3.0

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 methyl carbonate 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 吡啶 、 lithium aluminium deuteride 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (+/-)-1-[2H1]-Cyclopent-2-en-1-ol methyl carbonate
  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

• Analysis of Stereochemical Convergence in Asymmetric Pd-Catalysed Allylic Alkylation Reactions Complicated by Halide and Memory Effects
  作者：Ian J. S. Fairlamb、Guy C. Lloyd-Jones、Štěpán Vyskočil、Pavel Kočovský

  DOI：10.1002/1521-3765(20021004)8:19<4443::aid-chem4443>3.0.co;2-3

  日期：2002.10.4

  quantitative two-term description of memory effects arising in Pd-catalysed allylic alkylation reactions formally proceeding through 'meso'-type pi-allylpalladium intermediates is presented. The utility of this description (stereochemical convergence (sc) and global enantiomeric excess (ee(g))) is demonstrated by application to a series of Pd-catalysed allylic alkylation reactions involving racemic cyclopentenyl

  定量描述了在Pd催化的烯丙基烷基化反应中通过“介孔”型pi-烯丙基钯中间体正式进行的记忆效应的定量描述。通过将其应用于一系列涉及外消旋环戊烯基酯的Pd催化的烯丙基烷基化反应，证明了该描述的实用性（立体化学收敛（sc）和整体对映体过量（ee（g）））。通过使用一系列对映体纯的单膦配体对此类反应进行分析，可以得出结论，即在有效的记忆效应有效的情况下，在标准“基准”类型条件下获得的选择性（对映体过量（ee）值）可能会产生很大的误导性。但是，通过在一系列相关条件下比较给定配体/溶剂组合的sc和ee，可以预测当记忆效应被消除时将获得的极限（“潜在”）选择性。该技术以一种特定的配体（4b，“ MAP”）为例进行了说明，针对该配体采用了多种策略来寻找消除记忆效应并揭示该配体的有限选择性的条件。与使用标准非对映异构体平衡方法（例如添加的卤化物）所获得的条件相比，这些条件可提供更高的极限整体选择性。因此，s