ethyl α-cyano-α-fluorophenylacetate | 141716-61-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: ethyl α-cyano-α-fluorophenylacetate
• 英文别名: Ethyl 2-cyano-2-fluoro-2-phenylacetate
• CAS: 141716-61-2；358335-61-2
• 化学式: C₁₁H₁₀FNO₂
• 分子量: 207.204
• InChiKey: HZYMUAPGKPTYOO-UHFFFAOYSA-N

物化性质

• 沸点：
  291.4±35.0 °C(Predicted)
• 密度：
  1.184±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  50.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  ethyl α-cyano-α-fluorophenylacetate 、 仲丁醇 在 titanium(IV) isopropylate 作用下， 反应 2.0h， 以68%的产率得到2-butyl α-cyano-α-fluorophenylacetate
  参考文献：
  名称：

  Chemistry of novel compounds with multifunctional carbon structure. 9. Molecular design, synthetic studies, and NMR investigation of several efficient chiral derivatizing reagents which give very large 19F NMR .DELTA..delta. values in enantiomeric excess determination

  摘要：

  In order to develop efficient ee-determining reagents potentially superior to MTPA (1), some multifunctional compounds 2-5 were rationally designed. From NMR investigations of the analogous diastereomeric derivatives it was found that the chemical shift differences for each pair of diastereomers (DELTAdelta values) for CFPA derivatives 5d-f were approximately five times greater in F-19 NMR spectra and two times greater in H-1 NMR spectra than those of 1d-f. Synthesis of the optically pure CFPA, (-)-5a and (+)-5a, was achieved by nitrosation of each diastereomer of the optically active N-(1-phenylethyl)amides, 5f(M) and 5f(L), followed by thermal decomposition. Various derivatives were prepared by the condensation of 5b and lb with alcohol and amine nucleophiles, and both DELTAdelta(F) and DELTAdelta(H) Values were obtained for each compound. The CFPA derivatives 5d-m have proven to be significantly superior for ee determinations when compared to the corresponding MTPA derivatives 1d-m, particularly in compounds having remotely disposed chiral centers.

  DOI：

  10.1021/jo00059a036
• 作为产物：
  描述：

  苯基氰基乙酸乙酯 在 Selectfluor 作用下， 以 乙腈 为溶剂， 反应 4.5h， 生成 ethyl α-cyano-α-fluorophenylacetate
  参考文献：
  名称：

  开发钛-TADDOLate 催化的 β-酮酯不对称氟化。

  摘要：

  钛基路易斯酸通过亲电子 NF-氟化试剂催化 β-酮酯的 α-氟化。使用 TADDOL 的不对称催化二氯化钛 (TADDOL = α,α,α',α'-四芳基-(1,3-二氧戊环-4,5-二基)-二甲醇) 路易斯酸生成对映体富集的 α-氟化β - 对映体过量高达 91% 的酮酯，含 F-TEDA（1-氯甲基-4-氟-1,4-重氮二环[2.2.2] 辛烷双（四氟硼酸盐））乙腈溶液或 NFSI（N-氟苯磺酰亚胺）在二氯甲烷溶液中作为氟化试剂。研究了各种反应参数和 TADDOL 配体结构对催化活性和对映选择性的影响。通过相关性指定了几种氟化产物的绝对构型。获得了催化剂复合物通过氯化物解离电离的证据，随后生成了作为关键反应中间体的 β-酮烯醇钛。根据实验结果，提出了一般的机械示意图和感应的立体模型。

  DOI：

  10.3762/bjoc.7.166

文献信息

• Chemistry of novel compounds with multifunctional carbon structure. 9. Molecular design, synthetic studies, and NMR investigation of several efficient chiral derivatizing reagents which give very large 19F NMR .DELTA..delta. values in enantiomeric excess determination
  作者：Yoshio Takeuchi、Noriaki Itoh、Toshihiro Satoh、Toru Koizumi、Kentaro Yamaguchi

  DOI：10.1021/jo00059a036

  日期：1993.3

  In order to develop efficient ee-determining reagents potentially superior to MTPA (1), some multifunctional compounds 2-5 were rationally designed. From NMR investigations of the analogous diastereomeric derivatives it was found that the chemical shift differences for each pair of diastereomers (DELTAdelta values) for CFPA derivatives 5d-f were approximately five times greater in F-19 NMR spectra and two times greater in H-1 NMR spectra than those of 1d-f. Synthesis of the optically pure CFPA, (-)-5a and (+)-5a, was achieved by nitrosation of each diastereomer of the optically active N-(1-phenylethyl)amides, 5f(M) and 5f(L), followed by thermal decomposition. Various derivatives were prepared by the condensation of 5b and lb with alcohol and amine nucleophiles, and both DELTAdelta(F) and DELTAdelta(H) Values were obtained for each compound. The CFPA derivatives 5d-m have proven to be significantly superior for ee determinations when compared to the corresponding MTPA derivatives 1d-m, particularly in compounds having remotely disposed chiral centers.
• Development of the titanium–TADDOLate-catalyzed asymmetric fluorination of β-ketoesters
  作者：Lukas Hintermann、Mauro Perseghini、Antonio Togni

  DOI：10.3762/bjoc.7.166

  日期：——

  reagents. The effects of various reaction parameters and of the TADDOL ligand structure on the catalytic activity and enantioselectivity were investigated. The absolute configuration of several fluorination products was assigned through correlation. Evidence for ionization of the catalyst complex by chloride dissociation, followed by generation of titanium beta-ketoenolates as key reaction intermediates

  钛基路易斯酸通过亲电子 NF-氟化试剂催化 β-酮酯的 α-氟化。使用 TADDOL 的不对称催化二氯化钛 (TADDOL = α,α,α',α'-四芳基-(1,3-二氧戊环-4,5-二基)-二甲醇) 路易斯酸生成对映体富集的 α-氟化β - 对映体过量高达 91% 的酮酯，含 F-TEDA（1-氯甲基-4-氟-1,4-重氮二环[2.2.2] 辛烷双（四氟硼酸盐））乙腈溶液或 NFSI（N-氟苯磺酰亚胺）在二氯甲烷溶液中作为氟化试剂。研究了各种反应参数和 TADDOL 配体结构对催化活性和对映选择性的影响。通过相关性指定了几种氟化产物的绝对构型。获得了催化剂复合物通过氯化物解离电离的证据，随后生成了作为关键反应中间体的 β-酮烯醇钛。根据实验结果，提出了一般的机械示意图和感应的立体模型。