methyl 2-cyano-2-(4-fluorophenyl)acetate | 1190830-61-5

• 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: methyl 2-cyano-2-(4-fluorophenyl)acetate
• 英文别名: Methyl 2-cyano-2-(4-fluorophenyl)acetate
• CAS: 1190830-61-5
• 化学式: C₁₀H₈FNO₂
• 分子量: 193.177
• InChiKey: TUGMVBBQHSOFBL-UHFFFAOYSA-N

物化性质

• 沸点：
  284.4±25.0 °C(Predicted)
• 密度：
  1.229±0.06 g/cm3(Predicted)

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：
  0.2
• 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：

  methyl 2-cyano-2-(4-fluorophenyl)acetate 在 氨 、 氧气 、 N,N-二异丙基乙胺 、 三氯氧磷 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 24.0h， 生成 cyano(4-fluorophenyl)methyl diphenylphosphinate
  参考文献：
  名称：

  在二芳基膦氧化物存在下通过α-取代的丙二腈的好氧氧化制备O-保护的氰醇

  摘要：

  使用二芳基膦氧化物在O 2的存在下，实现了轻度，无氰化物的反应，并由易于获得的α-取代的丙二酸高效合成了O-膦酰基保护的氰醇。机理研究表明，除了丙二腈衍生物的初始有氧氧化外，该过程的显着特征还包括四面体中间体的形成和随后的分子内重排。可以通过醇解或通过用DIBAL-H还原来除去膦酰基保护基。

  DOI：

  10.1021/acs.orglett.9b00569
• 作为产物：
  描述：

  丙酮氰醇 、 methyl 2-diazo-2-(4-fluorophenyl)acetate 在 tetrakis(actonitrile)copper(I) hexafluorophosphate 、 三甲基氰硅烷 作用下， 以 二氯甲烷 为溶剂， 以73%的产率得到methyl 2-cyano-2-(4-fluorophenyl)acetate
  参考文献：
  名称：

  丙酮氰醇在α-芳基重氮乙酸铜的铜催化氢氰化反应中作为HCN的来源

  摘要：

  已经开发了使用丙酮氰醇作为氰化氢（HCN）源的Cu催化α-芳基重氮酸酯氢氰化的方法。已经发现，添加三甲基甲硅烷基氰化物（TMSCN）可以通过原位释放游离氰离子来显着加速转化，从而在温和条件下以高收率生产各种类型的α-芳基氰乙酸酯。

  DOI：

  10.1021/jo100356d

文献信息

• Diastereo- and enantioselective Mannich/cyclization cascade reaction of isocyanoacetates with cyclic sulfamide ketimines by cinchona alkaloid squaramide/AgOAc cooperative catalysis
  作者：Mei-Xin Zhao、Zhi-Wen Dong、Guang-Yu Zhu、Xiao-Li Zhao、Min Shi

  DOI：10.1039/c8ob01090k

  日期：——

  an efficient diastereo- and enantioselective Mannich/cyclization cascade reaction of α-substituted isocyanoacetates with 4-aryl-3-carbonyl-1,2,5-thiadiazole-1,1-dioxide type cyclic sulfamide ketimines cooperatively catalyzed by cinchona alkaloid-derived squaramide and AgOAc. The corresponding optically active 2,3,3a,4-tetrahydroimidazo[1,5-b][1,2,5]thiadiazole-1,1-dioxide derivatives were obtained

  我们已经开发了由金鸡纳生物碱协同催化的α-取代异氰基乙酸酯与4-芳基-3-羰基-1,2,5-噻二唑-1,1-二氧化物型环硫酰胺酮亚胺的高效非对映和对映选择性曼尼希/环化级联反应衍生的方胺和AgOAc。获得了相应的旋光性2,3,3a，4-四氢咪唑并[1,5- b ] [1,2,5]噻二唑-1,1-二氧化物衍生物，收率极高（高达99％）立体选择性（高达> 20：1 dr，高达94％ee）。
• Cinchona Alkaloid Squaramide-Catalyzed Asymmetric Michael Addition of α-Aryl Isocyanoacetates to β-Trifluoromethylated Enones and Its Applications in the Synthesis of Chiral β-Trifluoromethylated Pyrrolines
  作者：Mei-Xin Zhao、Hui-Kai Zhu、Tong-Lei Dai、Min Shi

  DOI：10.1021/acs.joc.5b01829

  日期：2015.11.20

  biologically attractive chiral β-trifluoromethylated pyrroline carboxylate in high yield via an isocyano group hydrolysis/cyclization/dehydration cascade reaction by treating with acid. The one-pot enantioselective Michael addition/isocyano group hydrolysis/cyclization/dehydration sequential protocol has also been investigated.

  金鸡纳生物碱方酰胺可有效催化α-芳基异氰基乙酸酯向β-三氟甲基化的烯酮的不对称迈克尔加成反应，从而为相应的加合物提供中等至良好收率的相邻的带有CF 3基团的手性叔碳中心和季碳中心，并且具有优异的收率。立体选择性。通过用酸处理，通过异氰基水解/环化/脱水级联反应，可以容易地以高收率容易地将加合物转化为生物学上有吸引力的手性β-三氟甲基化吡咯啉羧酸酯。还研究了一锅对映选择性迈克尔加成/异氰基水解/环化/脱水顺序规程。
• <i>Cinchona</i>Alkaloid-Derived Thiourea-Catalyzed Diastereo- and Enantioselective [3+2] Cycloaddition Reaction of Isocyanoacetates to Isatins: A Facile Access to Optically Active Spirooxindole Oxazolines
  作者：Mei-Xin Zhao、Hao Zhou、Wen-Hao Tang、Wei-Song Qu、Min Shi

  DOI：10.1002/adsc.201300077

  日期：2013.5.3

  An efficient diastereo‐ and enantioselective [3+2] cycloaddition reaction of α‐aryl isocyanoacetates to isatins catalyzed by a quinine‐derived bifunctional amine‐thiourea‐bearing sulfonamide as multiple hydrogen‐bonding donor catalyst has been investigated. The corresponding adducts, which bear a spirocyclic quaternary stereocenter at the C‐3 position of the oxindole, were obtained in good yields (51–95%)

  研究了由奎宁衍生的双官能胺-硫脲基磺酰胺作为多重氢键供体催化剂催化的α-芳基异氰基乙酸酯对异戊二烯的高效非对映和对映选择性[3 + 2]环加成反应。相应的加合物在羟吲哚的C-3位置带有螺环四级立体中心，获得的收率高（51–95％），非对映选择性高（高达> 20：1 dr）和良好至优异的对映选择性（最高到97％ee）。
• [EN] ROCK INHIBITORS AND USES THEREOF<br/>[FR] INHIBITEURS DE ROCK ET LEURS UTILISATIONS
  申请人：DIZAL JIANGSU PHARMACEUTICAL CO LTD

  公开号：WO2023226965A1

  公开（公告）日：2023-11-30

  Disclosed herein are compounds of Formula (I), and pharmaceutically acceptable salts thereof, that are useful as ROCK inhibitors. Also disclosed are pharmaceutical compositions comprising a compound of Formula (I), and methods of using such compounds or compositions to treat ROCK-related disorder (e.g., glaucoma).

  本文公开了可用作 ROCK 抑制剂的式 (I) 化合物及其药学上可接受的盐。还公开了包含式（I）化合物的药物组合物，以及使用此类化合物或组合物治疗 ROCK 相关疾病（如青光眼）的方法。
• Managing Highly Coordinative Substrates in Asymmetric Catalysis: A Catalytic Asymmetric Amination with a Lanthanum-Based Ternary Catalyst
  作者：Tomoyuki Mashiko、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1021/ja9052653

  日期：2009.10.21

  Full details of a catalytic asymmetric amination with a lanthanum/amide-based ligand catalyst system are described. A catalyst comprising La(NO3)(3)center dot 6H(2)O, (R)-3a and H-D-Val-V'Bu was identified to promote the catalytic asymmetric amination of nonprotected succinimide derivative 1 with as little as 1 mol % catalyst loading Mechanistic studies by various spectroscopic analyses and several control and kinetic experiments suggested that the catalyst components were in equilibrium between the associated and dissociated forms, and that the reaction likely proceeded through a La(NO3)(3)center dot 6H(2)O/(R)-3a/H-D-Val-O'Bu ternary complex. This catalyst system was also effective for asymmetric amination of N-nonsubstituted alpha-alkoxycarbonyl amides 7, hitherto unprecedented substrates in asymmetric catalysis, probably due to their attenuated reactivity and difficult stereocontrol, affording the amination products in up to > 99% yield and > 99% ee. The high catalytic performance and enantiocontrol of the reaction with highly coordinative substrates were achieved by the activation/recognition of the substrates exerted by coordination to lanthanum and hydrogen bonding cooperatively in the transition state.