ethyl 2-cyclopentylidene-2-fluoroacetate | 113307-25-8

• 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: ethyl 2-cyclopentylidene-2-fluoroacetate
• 英文别名: Ethyl 2-cyclopentylidene-2-fluoroacetate
• CAS: 113307-25-8
• 化学式: C₉H₁₃FO₂
• 分子量: 172.199
• InChiKey: RJFPFUUNAXBMAQ-UHFFFAOYSA-N

物化性质

• 沸点：
  219.9±15.0 °C(Predicted)
• 密度：
  1.103±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl 2-cyclopentylidene-2-fluoroacetate 在 氢氧化钾 、 O-(benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate 、 N,N-二异丙基乙胺 作用下， 以 甲醇 、 二氯甲烷 为溶剂， 反应 11.08h， 生成 2-Cyclopentylidene-2-fluoro-N-phenethyl-acetamide
  参考文献：
  名称：

  Fluoro-Olefins as Peptidomimetic Inhibitors of Dipeptidyl Peptidases

  摘要：

  The feasibility of the fluoro-olefin function as a peptidomimetic group in inhibitors for dipeptidyl peptidase IV and II (DPP IV and DPP II) is investigated by evaluation of N-substituted Gly-Psi[CF=C]pyrrolidines, Gly-Psi[CF=C]piperldines, and Gly-Psi[CF=C](2-cyano)pyrrolidines. Of this later class, the (Z)- and (E)-fluoro-olefin analogues were prepared and chemical stability in comparison with the parent amide was checked. Most of these compounds exhibited a strong binding preference toward DPP II with IC50 values in the low micromolar range, while only low DPP IV inhibitory potential is seen.

  DOI：

  10.1021/jm0495982
• 作为产物：
  描述：

  ethyl 2-fluoro-2-(1-hydroxycyclopentyl)-2-(phenylselanyl)acetate 在 三氟甲磺酸 作用下， 以 1,2-二氯乙烷 为溶剂， 反应 0.17h， 以59%的产率得到ethyl 2-cyclopentylidene-2-fluoroacetate
  参考文献：
  名称：

  Z-选择性或立体有择的烯基化反应：α-氟-α，β-不饱和酯的一种新合成方法

  摘要：

  使用顺-和/或反-3-芳基-2-氟-3-羟基-2-有机硒基乙酸酯3和4的脱硒酸实现α-氟-α,β-不饱和酯的Z-选择性形成三氟...

  DOI：

  10.1246/cl.2005.998

文献信息

• Photoenzymatic Generation of Unstabilized Alkyl Radicals: An Asymmetric Reductive Cyclization
  作者：Phillip D. Clayman、Todd K. Hyster

  DOI：10.1021/jacs.0c07918

  日期：2020.9.16

  Flavin-dependent 'ene'-reductases (ERED) can generate stabilized alkyl radicals when irradiated with visible light, however, they are not known to form unstabilized radicals. Here, we report an enantioselective radical cyclization using alkyl iodides as precursors to unstabilized nucleophilic radicals. Evidence suggests this species is accessed by photoexcitation of a charge-transfer complex that forms between flavin

  当用可见光照射时，黄素依赖性“烯”还原酶 (ERED) 可以产生稳定的烷基自由基，但是，不知道它们会形成不稳定的自由基。在这里，我们报告了使用烷基碘作为不稳定亲核自由基的前体的对映选择性自由基环化。有证据表明，该物种是通过光激发在黄素和蛋白质活性位点内的底物之间形成的电荷转移复合物而获得的。氢原子从黄素半醌到环化后形成的前手性自由基的立体选择性传递提供了跨各种底物的高水平的对映选择性。此外，我们发现氧化还原活性酯可用于代替烷基碘作为自由基前体。全面的，
• The Reaction of α-Diazo-β-hydroxy Esters with Boron Trifluoride Etherate:  Generation and Rearrangement of Destabilized Vinyl Cations. A Detailed Experimental and Theoretical Study
  作者：Roberto Pellicciari、Benedetto Natalini、Bahman M. Sadeghpour、Maura Marinozzi、James P. Snyder、Bobby L. Williamson、Jeffrey T. Kuethe、Albert Padwa

  DOI：10.1021/ja950971s

  日期：1996.1.1

  ketones. Further treatment of these α-diazo-β-hydroxy esters with boron trifluoride etherate in various solvents affords an unusual array of products. Product types and ratios were found to be strongly dependent on ring size and the solvent used. The reaction proceeds by Lewis acid complexation of the alcohol functionality of the diazo hydroxy ester with BF3 etherate followed by neighboring-group participation

  通过用 LDA 处理重氮乙酸乙酯，然后与一系列环酮反应来制备环状 2-重氮-3-羟基羧酸乙酯。在各种溶剂中用三氟化硼醚合物进一步处理这些 α-重氮-β-羟基酯，可得到一系列不寻常的产品。发现产品类型和比例很大程度上取决于环大小和所用溶剂。该反应通过重氮羟基酯的醇官能团与 BF3 醚合物的路易斯酸络合进行，然后重氮部分的相邻基团参与生成亚环烷基重氮盐。氮的损失会产生高反应性、不稳定的线性乙烯基阳离子。通过 1,2-亚甲基位移的扩环导致形成更稳定的弯曲环烯基乙烯基阳离子。随后的 1, 2-亚甲基位移导致环收缩，最终形成稳定的烯丙基阳离子。该阳离子要么被溶剂捕获，要么与相邻的离子发生环化...
• Scope and limitations of the Julia–Kocienski reaction with fluorinated sulfonylesters
  作者：Charlène Calata、Jean-Marie Catel、Emmanuel Pfund、Thierry Lequeux

  DOI：10.1016/j.tet.2009.03.041

  日期：2009.5

  The study of the Julia–Kocienski reaction between fluorinated arylsulfone and ketones is described. The corresponding fluoroalkenes were isolated in moderate to good yields from β- and δ-substituted cyclic ketones. From acyclic ketones and α-substituted cyclic ketones a decarbethoxylation reaction of the sulfonylesters occurred. This decarbethoxylation reaction opened a new route for the preparation

  描述了氟化芳基砜与酮之间的Julia-Kocienski反应的研究。从β-和δ-取代的环酮以中等至良好的产率分离出相应的氟代烯烃。由无环酮和α-取代的环酮发生磺酰基酯的脱碳乙氧基化反应。该脱碳乙氧基化反应为制备各种氟代烷基砜作为制备氟代烯烃的潜在基石开辟了一条新途径。
• Synthesis of (E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors
  作者：Pieter Van der Veken、István Kertèsz、Kristel Senten、Achiel Haemers、Koen Augustyns

  DOI：10.1016/s0040-4039(03)01542-9

  日期：2003.8

  (E)- and (Z)-fluoro-olefin analogues of potent dipeptidyl peptidase IV inhibitors were synthesized. A WadsworthHorner-Eminons reaction, followed by amide formation and reduction of the amide were used for the construction of the alpha-fluoro-alpha,beta-unsaturated amine functionality. (C) 2003 Elsevier Ltd. All rights reserved.

  （E）-和（Z）-氟化烯烃衍生物是以高效抑制Di-peptideyl peptidase IV活性为特征的抑制剂族。该文采用Wadsworth-Horner-Emmonds反应后，通过羰基形成与羰基还原的方式，构建了α-氟-α,β-不饱和胺基功能群。参考文献：Elsevier Ltd., 2003.
• Fluoroolefins as amide bond mimics in dipeptidyl peptidase IV inhibitors
  作者：Scott D. Edmondson、Lan Wei、Jinyou Xu、Jackie Shang、Shiyao Xu、Jianmei Pang、Ashok Chaudhary、Dennis C. Dean、Huaibing He、Barbara Leiting、Kathryn A. Lyons、Reshma A. Patel、Sangita B. Patel、Giovanna Scapin、Joseph K. Wu、Maria G. Beconi、Nancy A. Thornberry、Ann E. Weber

  DOI：10.1016/j.bmcl.2008.02.050

  日期：2008.4

  The synthesis, selectivity, rat pharmacokinetic profile, and drug metabolism profiles of a series of potent fluoroolefin-derived DPP-4 inhibitors (4) are reported. A radiolabeled fluoroolefin 33 was shown to possess a high propensity to form reactive metabolites, thus revealing a potential liability for this class of DPP-4 inhibitors. (C) 2008 Elsevier Ltd. All rights reserved.