cyclohex-2-enyl 3-oxobutanoate | 61363-92-6

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 酮酸及其衍生物
• 英文名称: cyclohex-2-enyl 3-oxobutanoate
• 英文别名: cyclohex-2-enyl acetoacetate；Δ²-Cyclohexenyl-acetoacetat；Cyclohex-2-en-1-yl 3-oxobutanoate
• CAS: 61363-92-6
• 化学式: C₁₀H₁₄O₃
• 分子量: 182.219
• InChiKey: IILVMUYVURNHSY-UHFFFAOYSA-N

物化性质

• 沸点：
  257.4±33.0 °C(Predicted)
• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.4
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.6
• 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：

  cyclohex-2-enyl 3-oxobutanoate 在 四(三苯基膦)钯 作用下， 以 苯 为溶剂， 反应 24.0h， 以87%的产率得到1-(2'-环己烯基)-2-丙酮
  参考文献：
  名称：

  Asymmetric Allylic Alkylation of Ketone Enolates:  An Asymmetric Claisen Surrogate

  摘要：

  The combination of catalytic palladium(0) and Trost ligand provides an effective catalyst for the rearrangement of allyl beta-ketoesters. The mechanism of the transformation involves formation of pi-allyl palladium intermediates which undergo enantioselective attack by ketone enolates. Decarboxylation of beta-ketocarboxylates allows regiospecific generation of enolates under extremely mild conditions.

  DOI：

  10.1021/ol048149t
• 作为产物：
  描述：

  bromoacetic acid cyclohex-2-enyl ester 在 samarium diiodide 作用下， 以 四氢呋喃 为溶剂， 反应 0.08h， 以74%的产率得到cyclohex-2-enyl 3-oxobutanoate
  参考文献：
  名称：

  SmI 2介导的β-酮酸酯的简便合成：Reformatsky反应类型的自缩合

  摘要：

  通过在温和条件下通过二碘化sa的自缩合反应将α-溴酸酯转化为β-酮酸酯。该反应似乎是通过形成Reformatsky反应类型的samariun diiodide酯烯酸酯引发的。

  DOI：

  10.1016/0040-4039(95)00127-x

文献信息

• Versatile Approaches for the Synthesis of Fused-Ring γ-Lactones Utilizing Cyclopropane Intermediates
  作者：Timothy R. Newhouse、Philip S. J. Kaib、Andrew W. Gross、E. J. Corey

  DOI：10.1021/ol400362t

  日期：2013.4.5

  A highly effective acid-catalyzed cyclopropyl ester to γ-lactone skeletal rearrangement has been demonstrated and applied to the synthesis of a variety of bi- and tricyclic functionalized lactones, rigid and highly compact structures for use as biological probes.

  已经证明了对γ-内酯骨架重排的高效酸催化的环丙基酯，并将其用于合成多种双环和三环官能化内酯，刚性和高度紧凑的结构，以用作生物探针。
• Nano CuFe₂O₄: an efficient, magnetically separable catalyst for transesterification of β-ketoesters
  作者：Mukut Gohain、Vinod Kumar、Johannes H. van Tonder、Hendrik C. Swart、Odireleng M. Ntwaeaborwa、Barend C. B. Bezuidenhoudt

  DOI：10.1039/c4ra15014g

  日期：——

  The preparation of a variety of β-ketoesters was achieved in high yields from methyl acetoacetate under neutral conditions through the utilization of magnetic CuFe₂O₄nanoparticles as catalyst.

  通过利用磁性CuFe2O4纳米颗粒作为催化剂，在中性条件下，从乙酰乙酸甲酯高产率地制备了各种β-酮酸酯。
• Stereospecific Angular Alkylation. A New Application of the Claisen Rearrangement¹
  作者：Albert W. Burgstahler、Ivan C. Nordin

  DOI：10.1021/ja01462a039

  日期：1961.1
• Palladium(II)-Catalyzed Cyclization of Unsaturated Hydroperoxides for the Synthesis of 1,2-Dioxanes
  作者：Jason R. Harris、Shelli R. Waetzig、K. A. Woerpel

  DOI：10.1021/ol901046z

  日期：2009.8.6

  The cyclization of gamma,delta-unsaturated tertiary hydroperoxides in the presence of a palladium(II) catalyst afforded 1,2-dioxanes resembling biologically active natural products. A variety of substrates were screened, and synthetic manipulations were accomplished to construct compounds with structural similarity to antimalarial targets.
• Yeast-mediated resolution of .beta.-keto esters of prochiral alcohols
  作者：Tomas Hudlicky、Toshiya Tsunoda、Kumar G. Gadamasetti、Jerry A. Murry、Gary E. Keck

  DOI：10.1021/jo00011a031

  日期：1991.5

  Several racemic alcohols were converted to their beta-keto esters with diketene, and the resulting compounds were subjected to kinetic resolution by means of bakers' yeast. The unreacted keto esters were separated from the reduced hydroxy esters by chromatography, and the products were analyzed for levels of enantiomeric excess. Chiral shift reagents, Mosher esters, and optical rotation of the enantiomers of the alcohols were the criteria used to determine the optical integrity of the resolved alcohols after hydrolysis of the esters. Absolute stereochemistry was determined for the resolution products of all the substrates. Some rationale is advanced to account for the observed levels of enantiomeric excess and for the apparent diastereospecificity of the enzymatic resolution. The utility of this process as means of resolution of prochiral alcohols as well as an application of such resolution to the preparation of both enantiomers of a pyrrolizidine alkaloid synthon are indicated.