1-deuteriocyclohex-2-en-1-yl acetate | 203798-11-2

• 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-deuteriocyclohex-2-en-1-yl acetate
• CAS: 203798-11-2
• 化学式: C₈H₁₂O₂
• 分子量: 141.174
• InChiKey: MQNAWGURFBPDMW-BNEYPBHNSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.66
• 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：
  0.62
• 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：

  1-deuteriocyclohex-2-en-1-yl acetate 在 四丙基溴化铵 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 以5%的产率得到(3-D)cyclohexene
  参考文献：
  名称：

  Hoffmann, Joachim; Holst, Hartmut; Volz, Wolfgang, Journal of Chemical Research, Miniprint, 1989, # 2, p. 401 - 428

  摘要：

  DOI：
• 作为产物：
  描述：

  1-deuteriocyclohex-2-en-1-ol 、 乙酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到1-deuteriocyclohex-2-en-1-yl acetate
  参考文献：
  名称：

  Memory and dynamics in Pd-catalyzed allylic alkylation with P,N-ligands

  摘要：

  The memory effect, known to exert a strong influence on selectivity in some applications of the Pd-catalyzed allylic alkylation, has been investigated for a catalytic system based on a bidentate P,N-ligand. Although this system might be expected to show strong memory effects due to the difference in the trans influence of the two donor atoms (P > N), isotopic labeling revealed an almost complete absence of regio-retention. Modeling of dynamic processes in the intermediate (eta(3)-allyl)Pd complex allowed this observation to be rationalized in terms of anion-assisted apparent rotation. The study has allowed seemingly conflicting reports on the behavior of (eta(3)-allyl)Pd systems to be unified by a computational model. (C) 2010 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2010.03.031

文献信息

• Retention of Regiochemistry of Allylic Esters in Palladium-Catalyzed Allylic Alkylation in the Presence of a MOP Ligand
  作者：Tamio Hayashi、Motoi Kawatsura、Yasuhiro Uozumi

  DOI：10.1021/ja973150r

  日期：1998.3.1

  In the palladium-catalyzed allylic alkylation of (E)-3-substituted-2-propenyl acetates (1), 1-substituted-2-propenyl acetates (2), and 1- or 3-deuterio-2-cyclohexenyl acetate (5), which proceeds through 1,3-unsymmetrically substituted π-allylpalladium intermediates, selective substitution at the position originally substituted with acetate was observed by use of a sterically bulky monodentate phosphine

  在钯催化的（E）-3-取代-2-丙烯基乙酸酯（1）、1-取代-2-丙烯基乙酸酯（2）和1-或3-氘代-2-环己烯基乙酸酯（5 )，通过 1,3-不对称取代的 π-烯丙基钯中间体进行，通过使用空间庞大的单齿膦配体 2-(二苯基膦基)-2'-甲氧基-1，观察到最初被乙酸酯取代的位置的选择性取代， 1'-联萘 (MeO-MOP)。通过将 [PdCl(π-环己烯基)]2 与 1 或 2 当量的 MeO-MOP (L*) 混合生成的 π-烯丙基钯配合物的结构研究表明，阳离子双膦配合物 [Pd(L*)2(π-环己烯基) )]+Cl-即使在存在过量配体的情况下也不会形成，但会形成中性单膦配合物 PdCl(L*)(π-环己烯基) (11)，使过量配体游离，并且 11 中 Cl 和 L* 的配位位点的交换比三苯基膦配合物 PdCl(PPh3)(π-环己烯基) (13) 中的交换要慢得多。缓慢的交流可以理性.
• Palladium-catalyzed asymmetric coupling reactions between allylic acetates and organozinc reagents. Mechanistic implications
  作者：Jean-Claude Fiaud、Louisa Aribi-Zouioueche

  DOI：10.1016/0022-328x(85)80323-5

  日期：1985.11

  Asymmetric induction and deuterium distribution studies have provided information about the mechanism of the palladium-catalyzed coupling reaction between allylic acetates and phenylzinc chloride, namely the presence of a symmetric η3-allylic ligand in the intermediate, probably along with a monodentate phosphine ligand.

  不对称诱导和氘分布的研究已经提供了有关的机制的信息的钯催化偶合烯丙基乙酸酯和氯化phenylzinc，即对称的η之间存在反应3在中间-烯丙基配体，可能与单齿膦配位体一起。
• Copper-Catalyzed Asymmetric Allylic Alkylation of Racemic Cyclic Substrates: Application of Dynamic Kinetic Asymmetric Transformation (DYKAT)
  作者：Jean-Baptiste Langlois、Alexandre Alexakis

  DOI：10.1002/adsc.200900790

  日期：2010.2.15

  The copper-catalyzed asymmetric allylic alkylation (AAA) is of great interest in organic synthesis. This reaction was extensively studied using a broad range of substrates, ligands and organometallic reagents. However, the use of racemic substrates was still limited. Although some processes of kinetic resolution are reported in the literature, no examples of quantitative deracemization are described

  铜催化的不对称烯丙基烷基化（AAA）在有机合成中非常重要。使用各种各样的底物，配体和有机金属试剂对这一反应进行了广泛的研究。但是，外消旋底物的使用仍然受到限制。尽管在文献中报道了一些动力学拆分方法，但是没有描述定量脱氨的实例，如Pd催化的烯丙基烷基化的情况。在此，我们将通过在铜催化的AAA中开发这种方法的第一个实例来全面介绍我们的研究。本文报道了高对映选择性（高达99％ee），反应范围和机理考虑。
• Catalytic Allylic C−H Acetoxylation and Benzoyloxylation via Suggested (η³-Allyl)palladium(IV) Intermediates
  作者：Lukasz T. Pilarski、Nicklas Selander、Dietrich Böse、Kálmán J. Szabó

  DOI：10.1021/ol9023369

  日期：2009.12.3

  Palladium-catalyzed allylic acetoxylations and benzoyloxylations were carried out using iodonium salts. The reactions proceed under mild conditions with high regio- and stereoselectivity. The catalysis can be performed under both acidic and nonacidic conditions without use of BQ or other external oxidants and activator ligands. Deuterium labeling experiments clearly show that the catalytic reaction

  使用碘鎓盐进行钯催化的烯丙基乙酰氧基化和苯甲酰氧基化。反应在温和条件下以高区域选择性和立体选择性进行。该催化反应可以在酸性和非酸性条件下进行，而无需使用BQ或其他外部氧化剂和活化剂配体。氘标记实验清楚地表明，通过（η催化反应进行3 -烯丙基）钯中间体。用一种催化剂进行的化学计量研究为形成Pd（IV）物种提供了证据。
• Mechanism of Palladium-Catalyzed Allylic Acetoxylation of Cyclohexene
  作者：Helena Grennberg、Jan-E. Bäckvall

  DOI：10.1002/(sici)1521-3765(19980615)4:6<1083::aid-chem1083>3.0.co;2-f

  日期：1998.6.15