ethyl (R)-1-(prop-2-enyl)-2-oxocyclopentanecarboxylate | 156991-64-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: ethyl (R)-1-(prop-2-enyl)-2-oxocyclopentanecarboxylate
• 英文别名: (1R)-(-)-ethyl 1-allyl-2-oxocyclopentanecarboxylate；(R)-ethyl 1-allyl-2-oxocyclopentanecarboxylate；ethyl (1R)-2-oxo-1-prop-2-enylcyclopentane-1-carboxylate
• CAS: 156991-64-9
• 化学式: C₁₁H₁₆O₃
• 分子量: 196.246
• InChiKey: HMHXLPLTOMZUKK-NSHDSACASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.8
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (R)-1-(prop-2-enyl)-2-oxocyclopentanecarboxylate 在 (acetylacetonato)dicarbonylrhodium (l) 、 Jones reagent 、 三甲基氯硅烷 、 BINAPa 、 氢气 作用下， 以 丙酮 、 甲苯 为溶剂， 80.0 ℃ 、2.03 MPa 条件下， 反应 21.0h， 生成 ethyl (1R)-1-(4-methoxy-4-oxobutyl)-2-oxocyclopentane-1-carboxylate
  参考文献：
  名称：

  对映纯螺[4,4]壬烷-1,6-二酮的实用不对称合成

  摘要：

  报道了一种对映体纯的螺[4,4]壬烷-1,6-二酮的实用不对称合成，对映体是手性配体发展的重要前体。该合成策略包括通过以面包酵母为主要还原步骤，通过生物还原对具有手性季碳中心的易于合成的酮前体进行动力学拆分，然后进行加氢甲酰化，氧化，酯化和狄克曼环化反应序列以生成螺五元环。结果发现，对映体纯的1-烯丙基-2-氧代环戊烷羧酸乙酯的β-酮羰基的掩蔽通过在Dieckmann缩合过程中，必须与1，3-二醇衍生物形成缩酮，以防止其在基本条件下外消旋化。该方法可以以克级规模制备螺环[4,4]壬烷-1,6-二酮（1）的两种对映体（1），具有优异的对映纯度（高达> 99％ee），总产率为54％[（R） ‐ 1 ]和42％[（S）‐ 1 ]。本合成方法的实用性为开发基于螺[4,4]壬烷-1,6-二酮的手性化学提供了基础平台。

  DOI：

  10.1002/adsc.201100089
• 作为产物：
  描述：

  1-allyl-2-oxo-cyclopentanecarboxylic acid ethyl ester 生成 ethyl (R)-1-(prop-2-enyl)-2-oxocyclopentanecarboxylate
  参考文献：
  名称：

  Reassignment of the absolute configuration of the baker's yeast reduction of (±)-ethyl 1-allyl-2-oxocyclopentanecarboxylate

  摘要：

  The baker's yeast reduction of(+/-)-ethyl 1-allyl-2-oxocyclopentanecarboxylate under aqueous conditions in the presence of CuO yields (1S,2S)-(+)-ethyl 1-allyl-2-hydroxycyclopentanecarboxylate and the unreacted enantiomer (1R)-(-)-ethyl 1-allyl-2-oxocyclopentanecarboxylate. The absolute configuration of the secondary alcohol was determined from the X-ray crystal structure of the (1S)- 10-camphorsulfonyl derivative of (1S,2S)-(+)-ethyl 1-allyl-2-hydroxycyclopentanecarboxylate. This refutes configurational claims based on CD/ORD and chemical affiliation techniques currently reported in the literature for this reaction. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00334-1

文献信息

• Chiral α-Amino Acid/Palladium-Catalyzed Asymmetric Allylation of α-Branched β-Ketoesters with Allylic Amines: Highly Enantioselective Construction of All-Carbon Quaternary Stereocenters
  作者：Ya-Nan Xu、Meng-Zeng Zhu、Shi-Kai Tian

  DOI：10.1021/acs.joc.9b02282

  日期：2019.11.15

  use of allylic amines as allylating agents in the chiral α-amino acid/palladium-catalyzed asymmetric allylation of α-branched β-ketoesters, providing highly enantioselective access to all-carbon quaternary stereocenters. Notably, the formation of a primary amine, a secondary amine, or ammonia as a byproduct has little influence on the enantioselectivity for the catalytic asymmetric synthesis of structurally

  已经开发出一种新的协议，用于将烯丙基胺用作α-支链β-酮酸酯的手性α-氨基酸/钯催化的不对称烯丙基化中的烯丙基化剂，从而提供了对映全碳全季铵立体中心的高度对映选择性。值得注意的是，作为副产物的伯胺，仲胺或氨的形成对结构多样的α，α-二取代的β-酮酯的催化不对称合成的对映选择性几乎没有影响。
• Asymmetric Allylation of 2-Oxocycloalkanecarboxylates
  作者：Masanori Yoshida、Shohei Yano、Shoji Hara

  DOI：10.1055/s-0036-1588095

  日期：——

  this study, the highly enantioselective α-allylation of α-substituted β-ketoesters, particularly 2-oxocycloalkanecarboxylates, is achieved by synergistic catalysis with an achiral palladium complex and a chiral primary amino acid. Various α-allylated β-ketoesters containing a quaternary carbon stereogenic center are synthesized in high yields (up to 97%) with excellent enantioselectivity (up to 99% ee)

  摘要 在该研究中，通过与非手性钯配合物和手性伯氨基酸的协同催化作用，可以实现α-取代的β-酮酸酯，特别是2-氧代环烷羧酸酯的高度对映选择性的α-烯丙基化。以高收率（最高97％）和出色的对映选择性（最高ee高达99％）合成了各种含有季碳立体生成中心的α-烯丙基化的β-酮酸酯。 在该研究中，通过与非手性钯配合物和手性伯氨基酸的协同催化作用，可以实现α-取代的β-酮酸酯，特别是2-氧代环烷羧酸酯的高度对映选择性的α-烯丙基化。以高收率（最高97％）和出色的对映选择性（最高ee高达99％）合成了各种含有季碳立体生成中心的α-烯丙基化的β-酮酸酯。
• Synthesis and applications of (1 R ,5 S ,6 S )-6-(2,2-dimethylpropanamido)spiro[4.4]nonan-1-ol as a chiral auxiliary in Diels–Alder reactions
  作者：Michael J. Burke、Murray M. Allan、Masood Parvez、Brian A. Keay

  DOI：10.1016/s0957-4166(00)00242-1

  日期：2000.7

  2-dimethylpropanamido)spiro[4.4]nonan-1-ol 7 is described along with its application as a chiral auxiliary in various Diels–Alder reactions. The enantioselectivity of the Diels–Alder adducts ranged from 86–98% ee. The Diels–Alder adducts were easily removed from the chiral auxiliary and the latter was recyclized. The absolute and relative stereochemistry of 7 was determined from an X-ray crystal structure of the

  （1 R，5 S，6 S）-6-（2,2-二甲基丙酰胺基）spiro [4.4] nonan-1-ol 7的短时不对称合成及其在各种Diels–Alder中作为手性助剂的应用反应。Diels–Alder加合物的对映选择性为ee的86–98％。狄尔斯-阿尔德加合物很容易从手性助剂中除去，后者被回收利用。的绝对和相对立体化学7从的X射线晶体结构确定p的-bromobenzoate衍生物7。
• Enantioselective Palladium-Catalyzed Decarboxylative Allylation of β-Keto Esters Assisted by a Thiourea
  作者：Lung Chung、Xumu Zhang、Hua Qian、Guoxian Gu、Qinghai Zhou、Jiaxiang Lu

  DOI：10.1055/s-0036-1590869

  日期：2018.1

  decarboxylative allylation of β-keto esters catalyzed by a palladium bis(phosphine)-thiourea complex is reported. This procedure is not only effective for β-keto esters, but also effective for β-keto amides. An intermolecular variant of the asymmetric decarboxylative allylation is also established. DFT calculations indicate that an outer-sphere mechanism is viable for the decarboxylative allylation

  报道了由钯双（膦）-硫脲复合物催化的 β-酮酯的对映选择性分子内脱羧烯丙基化。该程序不仅对β-酮酯有效，而且对β-酮酰胺有效。还建立了不对称脱羧烯丙基化的分子间变体。DFT 计算表明，外球机制对于 β-酮酯的脱羧烯丙基化是可行的。
• Enantioselective synthesis of spiro[4.4]non- and spiro[4.5]dec-2-ene-1,6-diones
  作者：B. Chitkul、Y. Pinyopronpanich、C. Thebtaranonth、Y. Thebtaranonth、W.C. Taylor

  DOI：10.1016/s0040-4039(00)79975-8

  日期：1994.2

  Spiro[4.4]non- and spiro[4.5]dec-2-ene-1,6-diones [2; n = 0 and 1] were prepared in moderate to high enantiomeric purities via asymmetric allylation of enamines 6 and ketal derivatives 7 and 8 formed from keto-esters 5, followed by a carbanionic cyclization process.

  螺[4.4]非螺和螺[4.5]癸-2-烯-1,6-二酮[ 2 ; n = 0和1]通过烯胺6和由酮酸酯5形成的缩酮衍生物7和8的不对称烯丙基化，以中等至高对映体纯度进行制备，然后进行碳负离子环化过程。