(R)-ethyl 1-fluoro-2-oxocyclopentanecarboxylate | 124170-32-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (R)-ethyl 1-fluoro-2-oxocyclopentanecarboxylate
• 英文别名: ethyl 1-fluoro-2-oxocyclopentane-1-carboxylate；ethyl 2-fluorocyclopentanone-2-carboxylate；Ethyl (1R)-1-fluoro-2-oxocyclopentanecarboxylate；ethyl (1R)-1-fluoro-2-oxocyclopentane-1-carboxylate
• CAS: 124170-32-7
• 化学式: C₈H₁₁FO₃
• 分子量: 174.172
• InChiKey: PTZFYJUFLYSVIV-MRVPVSSYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.1
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  43.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  2-氧代环戊羧酸乙酯 在 copper(II) bis(trifluoromethanesulfonate) 、 N-氟代双苯磺酰胺 、 bis-[2-((4S)-4-phenyl-4,5-dihydro-oxazol-2-yl)-phenyl]-amine 作用下， 以 neat (no solvent) 为溶剂， 反应 0.07h， 以96%的产率得到(R)-ethyl 1-fluoro-2-oxocyclopentanecarboxylate
  参考文献：
  名称：

  在球磨机中由手性铜配合物催化的快速，无溶剂和高对映选择性氟化的小β-酮酯

  摘要：

  使用行星式球磨机已经开发了在无溶剂条件下由二苯胺连接的双（恶唑啉）-Cu（OTf）2络合物催化的快速和高度对映选择性氟化的小β-酮酸酯。

  DOI：

  10.1039/c6gc03306g

文献信息

• Reagent-controlled enantioselectivity switch for the asymmetric fluorination of β-ketocarbonyls by chiral primary amine catalysis
  作者：Yang'en You、Long Zhang、Sanzhong Luo

  DOI：10.1039/c6sc03109a

  日期：——

  enantioselectivity switch was uncovered in the asymmetric α-fluorination of β-ketocarbonyls by a chiral primary amine catalyst. By a simple swap of fluorination reagents, both enantiomers of the quaternary fluorination adducts could be obtained with good yields and high enantioselectivity. Mechanistic studies disclosed dual H-bonding and electrostatic stereocontrolling modes for the catalysis.

  通过手性伯胺催化剂在β-酮羰基的不对称α-氟化反应中未发现试剂控制的对映选择性开关。通过简单地交换氟化试剂，可以以良好的产率和高的对映选择性获得季氟化加合物的两种对映异构体。机理研究揭示了催化的双重氢键结合和静电立体控制方式。
• Enantioselective Halogenation of β-Oxo Esters Catalyzed by a Chiral Sulfoximine-Copper Complex
  作者：Marcus Frings、Carsten Bolm

  DOI：10.1002/ejoc.200900467

  日期：2009.8

  A C1-symmetric amino sulfoximine has been used as a chiral ligand in copper-catalyzed asymmetric halogenation reactions of β-oxo esters. Both the catalyst itself and the reaction conditions were optimized, and 26 fluorinated, chlorinated, and brominated products were obtained with enantioselectivities of up to 91 % ee in yields of up to 99 %. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany

  在铜催化的 β-氧代酯的不对称卤化反应中，C1 对称氨基亚砜亚胺已用作手性配体。对催化剂本身和反应条件进行了优化，获得了 26 种氟化、氯化和溴化产物，对映选择性高达 91% ee，产率高达 99%。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Syntheses and Applications of (Thio)Urea-Containing Chiral Quaternary Ammonium Salt Catalysts
  作者：Johanna Novacek、Mario Waser

  DOI：10.1002/ejoc.201301594

  日期：2014.2

  bifunctional (thio)urea-containing quaternary ammonium salts based on easily obtainable chiral backbones. Among the different classes of catalysts that were successfully synthesized, those based on trans-1,2-cyclohexane diamine were found to be the most powerful for the asymmetric α-fluorination of β-keto esters. Selectivities up to 93:7 could be obtained by using only 2 mol-% of the optimized catalyst. The

  我们在此报告了我们基于易于获得的手性骨架获得一类新的系统修饰的含（硫）脲的季铵盐的努力。在成功合成的不同类别的催化剂中，发现基于反式-1,2-环己二胺的催化剂对β-酮酯的不对称α-氟化作用最强。仅使用 2 mol-% 的优化催化剂即可获得高达 93:7 的选择性。这些催化剂的双功能性质的重要性通过使用简化的单功能催化剂类似物的对照实验得到证明，该类似物仅产生几乎外消旋的产物。
• Enantioselective α-Fluorination and Chlorination of β-Ketoesters by Cobalt Catalyst
  作者：Motoi Kawatsura、Shunsuke Hayashi、Yuji Komatsu、Shuichi Hayase、Toshiyuki Itoh

  DOI：10.1246/cl.2010.466

  日期：2010.5.5

  We demonstrated the cobalt-catalyzed asymmetric α-fluorination and α-chlorination of β-ketoesters. Both reactions were achieved using a catalytic amount of Co(acac)2 with (R,R)-Jacobsen’s salen ligand; α-fluorinated or α-chlorinated products were thus obtained with a good enentioselectivity.

  我们展示了钴催化的不对称 α-氟化和 α-氯化 β-酮酯反应。这两个反应都是使用催化量的 Co(acac)2 与 (R,R)-Jacobsen's salen 配体实现的；从而以良好的烯选择性获得了 α-氟化或 α-氯化产物。
• SPANamine derivatives in the catalytic asymmetric α-fluorination of β-keto esters
  作者：Olivier Jacquet、Nicolas D. Clément、Zoraida Freixa、Aurora Ruiz、Carmen Claver、Piet W.N.M. van Leeuwen

  DOI：10.1016/j.tetasy.2011.08.023

  日期：2011.7

  The use of C-2-symmetric enantiopure nitrogen ligands in the asymmetric catalytic alpha-fluorination of beta-ketoesters is described. SPANamine 1 in the presence of nickel salts gives up to 63% ee in the fluorination of tert-butyl 2-oxocyclopentanecarboxylate with N-fluorosuccinimide (NFSI). The same enantioselectivity is obtained when SPANamine 1 is used as an organocatalyst, although the reaction is much slower. (C) 2011 Elsevier Ltd. All rights reserved.