(R)-ethyl 1-fluoro-2-oxocyclohexanecarboxylate | 1253858-56-8

• 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-oxocyclohexanecarboxylate
• 英文别名: ethyl 1-fluoro-2-oxocyclohexane-1-carboxylate；ethyl (R)-1-fluoro-2-oxocyclohexane-1-carboxylate；(R)-ethyl 1-fluoro-2-oxocyclopentanecarboxylate；(R)-ethyl 2-fluoro-2-cyclohexanonecarboxylate；ethyl (1R)-1-fluoro-2-oxocyclohexane-1-carboxylate
• CAS: 1253858-56-8
• 化学式: C₉H₁₃FO₃
• 分子量: 188.199
• InChiKey: WBRNDLRGLOAFCQ-SECBINFHSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.78
• 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-环己酮甲酸乙酯 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95%的产率得到(R)-ethyl 1-fluoro-2-oxocyclohexanecarboxylate
  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

• 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)
• 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。
• Recyclable fluorous cinchona alkaloid ester as a chiral promoter for asymmetric fluorination of β-ketoesters
  作者：Wen-Bin Yi、Xin Huang、Zijuan Zhang、Dian-Rong Zhu、Chun Cai、Wei Zhang

  DOI：10.3762/bjoc.8.138

  日期：——

  A fluorous cinchona alkaloid ester has been developed as a chiral promoter for the asymmetric fluorination of β-ketoesters. It has comparable reactivity and selectivity to the nonfluorous versions of cinchona alkaloids and can be easily recovered from the reaction mixture by simple fluorous solid-phase extraction (F-SPE) and used for the next round of reaction without further purification.

  一种氟疏芸香碱酯已经被开发出来，作为手性促进剂用于β-酮酯的不对称氟化反应。它与非氟疏版本的芸香碱碱都具有可比较的反应性和选择性，并且可以通过简单的氟疏固相萃取（F-SPE）从反应混合物中轻松回收，并在不需进一步纯化的情况下用于下一轮反应。
• Alkali Carbonates Improve β,β-Diaryl Serine-Catalyzed Enantioselective α-Fluorination of β-Dicarbonyl Compounds
  作者：Katsuki Endo、Daiki Tomon、Satoru Arimitsu

  DOI：10.1021/acs.joc.3c00730

  日期：2023.7.7

  cyclic and acyclic β-dicarbonyl compounds, including β-diketones, β-ketoesters, and β-ketoamides. The reactions with β,β-diaryl serines as primary amine organocatalysts were enhanced by adding alkali carbonates, such as Na2CO3 or Li2CO3, and enabled the reaction to be conducted with only 1.1 equiv of Selectfluor. The optimal conditions afforded the α-fluorinated β-dicarbonyl compounds in 50–99% yield

  在此，我们报道了环状和无环β-二羰基化合物（包括β-二酮、β-酮酯和β-酮酰胺）的高度对映选择性α-氟化。通过添加碱金属碳酸盐，例如Na 2 CO 3或Li 2 CO 3 ，可以增强以β,β-二芳基丝氨酸作为伯胺有机催化剂的反应，并且使得反应能够仅用1.1当量的Selectflu进行。最佳条件提供了 α-氟化 β-二羰基化合物，产率为 50-99%，具有优异的对映选择性（高达 98% ee）。
• Enantioselective fluorination of β-ketoesters using tartrate derived bidentate bioxazoline-Cu(II) complexes
  作者：Kaluvu Balaraman、Ravichandran Vasanthan、Venkitasamy Kesavan

  DOI：10.1016/j.tetasy.2013.07.004

  日期：2013.8

  Enantioselective fluorination of aliphatic cyclic and acyclic beta-ketoesters was achieved in excellent yield (up to 98%) with moderate to good enantioselectivities (up to 86% ee) using tartrate derived bidentate bioxazoline-Cu(II) complexes. This is the first report of a bioxazoline which forms a 5-membered chelate inducing enantioselectivity in the asymmetric fluorination of beta-ketoesters. (C) 2013 Elsevier Ltd. All rights reserved.