(S)-tert-butyl 1-fluoro-2-oxo-cyclopentanecarboxylate

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (S)-tert-butyl 1-fluoro-2-oxo-cyclopentanecarboxylate
• 英文别名: tert-butyl (1S)-1-fluoro-2-oxocyclopentane-1-carboxylate
• 化学式: C₁₀H₁₅FO₃
• 分子量: 202.226
• InChiKey: ZFDLHKCZQAYUNW-JTQLQIEISA-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：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 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：

  tert-butyl 2-oxocyclopentanecarboxylate 在 (4S)-2-[6-(13-azapentacyclo[13.8.0.02,11.03,8.018,23]tricosa-1(15),2(11),3,5,7,9,16,18,20,22-decaen-13-ylmethyl)pyridin-2-yl]-4-propan-2-yl-4,5-dihydro-1,3-oxazole 、 nickel(II) perchlorate 、 N-氟代双苯磺酰胺 作用下， 以 二氯甲烷 为溶剂， 反应 24.0h， 以90%的产率得到(S)-tert-butyl 1-fluoro-2-oxo-cyclopentanecarboxylate
  参考文献：
  名称：

  路易斯酸催化 β-酮酯的不对称氟化：通过改变操作顺序显着提高对映选择性

  摘要：

  使用杂化手性恶唑啉配体 1 实现了 β-酮酯的高效路易斯酸催化不对称氟化和氯化。

  DOI：

  10.1246/cl.2008.1098

文献信息

• Chiral bifunctional phase transfer catalysts for asymmetric fluorination of β-keto esters
  作者：Xisheng Wang、Quan Lan、Seiji Shirakawa、Keiji Maruoka

  DOI：10.1039/b920099a

  日期：——

  Chiral bifunctional phase transfer catalysts introducing bis(diarylhydroxymethyl) substituents at 3,3′-positions of the chiral binaphthyl core were successfully applied to asymmetric fluorination of cyclic β-keto esters with high enantioselectivities.

  具有二芳基羟甲基取代基的手性双功能相转移催化剂在手性二萘基核心的3,3'-位成功应用于循环β-酮酯的非对称氟化反应，显示出高的对映选择性。
• 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。
• Highly enantioselective fluorination reactions of β-ketoesters and β-ketophosphonates catalyzed by chiral palladium complexes
  作者：Yoshitaka Hamashima、Toshiaki Suzuki、Hisashi Takano、Yuta Shimura、Yasunori Tsuchiya、Ken-ichi Moriya、Tomomi Goto、Mikiko Sodeoka

  DOI：10.1016/j.tet.2005.12.070

  日期：2006.7

  Using chiral palladium enolates as key intermediates, efficient catalytic enantioselective fluorination reactions of active methine compounds have been developed. These reactions can be conducted in alcoholic solvents without any precaution to exclude water and moisture, and various β-ketoesters and β-ketophosphonates were fluorinated in a highly enantioselective manner (up to 98% ee).

  使用手性钯烯醇盐作为关键中间体，已经开发了活性次甲基化合物的有效催化对映选择性氟化反应。这些反应可以在酒精溶剂中进行，无需任何预防措施即可排除水和湿气，并且各种β-酮酸酯和β-酮膦酸酯以高度对映选择性的方式被氟化（至多98％ee）。
• Immobilization and Reuse of Pd Complexes in Ionic Liquid:  Efficient Catalytic Asymmetric Fluorination and Michael Reactions with β-Ketoesters
  作者：Yoshitaka Hamashima、Hisashi Takano、Daido Hotta、Mikiko Sodeoka

  DOI：10.1021/ol035053a

  日期：2003.9.1

  [reaction: see text] Palladium complexes (1 and 2) were immobilized in ionic liquids, and their applications to catalytic asymmetric fluorination and Michael reaction of beta-ketoesters were successfully demonstrated. This immobilization enabled the reuse of the catalysts no less than 10 times in fluorination and 5 times in Michael reaction with levels of efficiency comparable to those obtained in

  [反应：见正文]将钯配合物（1和2）固定在离子液体中，并成功证明了其在催化不对称氟化和β-酮酸酯的迈克尔反应中的应用。这种固定化使得催化剂的再利用在氟化中的重复使用率不低于10次，在迈克尔反应中的重复使用率不低于5次，其效率水平可与常规有机溶剂中获得的水平相媲美。