甲基(4-氟苯基)(异氰基)乙酸酯 | 730964-78-0

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 中文名称: 甲基(4-氟苯基)(异氰基)乙酸酯
• 英文名称: methyl 2-isocyano-2-(4-fluorophenyl)acetate
• 英文别名: 2-Isocyano-2-(4-fluorophenyl) acetic acid methyl ester；methyl 2-(4-fluorophenyl)-2-isocyanoacetate
• CAS: 730964-78-0
• 化学式: C₁₀H₈FNO₂
• mdl: MFCD04117561
• 分子量: 193.177
• InChiKey: MHBBFMUEGZAVGC-UHFFFAOYSA-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：
  0.2
• 拓扑面积：
  30.7
• 氢给体数：
  0
• 氢受体数：
  4

安全信息

• 海关编码：
  2926909090

反应信息

• 作为反应物：
  描述：

  甲基(4-氟苯基)(异氰基)乙酸酯 在 水 、 对甲苯磺酸 、 三乙胺 作用下， 以 叔丁醇 为溶剂， 反应 24.0h， 生成 methyl 4-(4-fluorophenyl)-2-oxo-1,3-oxazinane-4-carboxylate
  参考文献：
  名称：

  Triple Role of Phenylselenonyl Group Enabled a One-Pot Synthesis of 1,3-Oxazinan-2-ones From α-Isocyanoacetates, Phenyl Vinyl Selenones, and Water

  摘要：

  Reaction of alpha-substituted alpha-isocyanoacetates with phenyl vinyl selenones in the presence of a catalytic amount of base (DBU or Et3N, 0.05-0.1 equiv) followed by addition of p-toluenesulfonic acid (PTSA, 0.1-0.2 equiv) afforded 4,4,5-trisubstituted 1,3-oxazinan-2-ones in good to excellent yields. Enantiomerically enriched heterocycles can also be prepared using a Cinchona alkaloid-derived bifunctional organocatalyst for the Michael addition step. The phenylselenonyl group served as an activator for the Michael addition, a leaving group and a latent oxidant in this integrated reaction sequence.

  DOI：

  10.1021/ja506031h
• 作为产物：
  描述：

  2-(4-氟苯基)-2-甲酰胺基乙酸甲酯 在 二异丙胺 、 三氯氧磷 作用下， 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 甲基(4-氟苯基)(异氰基)乙酸酯
  参考文献：
  名称：

  Triple Role of Phenylselenonyl Group Enabled a One-Pot Synthesis of 1,3-Oxazinan-2-ones From α-Isocyanoacetates, Phenyl Vinyl Selenones, and Water

  摘要：

  Reaction of alpha-substituted alpha-isocyanoacetates with phenyl vinyl selenones in the presence of a catalytic amount of base (DBU or Et3N, 0.05-0.1 equiv) followed by addition of p-toluenesulfonic acid (PTSA, 0.1-0.2 equiv) afforded 4,4,5-trisubstituted 1,3-oxazinan-2-ones in good to excellent yields. Enantiomerically enriched heterocycles can also be prepared using a Cinchona alkaloid-derived bifunctional organocatalyst for the Michael addition step. The phenylselenonyl group served as an activator for the Michael addition, a leaving group and a latent oxidant in this integrated reaction sequence.

  DOI：

  10.1021/ja506031h

文献信息

• Catalytic Enantioselective Michael Addition of α-Aryl-α-Isocyanoacetates to Vinyl Selenone: Synthesis of α,α-Disubstituted α-Amino Acids and (+)- and (−)-Trigonoliimine A
  作者：Thomas Buyck、Qian Wang、Jieping Zhu

  DOI：10.1002/anie.201306663

  日期：2013.11.25

  title reaction in the presence of the catalyst 1 afforded Michael adducts in excellent yields and enantioselectivities. The adducts were readily converted into α,α′‐disubstituted α‐amino acids. The enantioselective total synthesis of both (+)‐ and (−)‐trigonoliimine A was accomplished using one of the Michael adducts derived from this methodology. M.S.=molecular sieves.

  就像迈克：在催化剂1的存在下进行标题反应，可以以出色的收率和对映选择性提供迈克尔加合物。加合物易于转化为α，α'-二取代的α-氨基酸。（+）-和（-）-三角果碱亚胺A的对映选择性全合成是使用衍生自该方法的迈克尔加合物之一完成的。MS ＝分子筛。
• Silver-Catalyzed Asymmetric Desymmetrization of Cyclopentenediones via [3 + 2] Cycloaddition with α-Substituted Isocyanoacetates
  作者：Jimil George、Hun Young Kim、Kyungsoo Oh

  DOI：10.1021/acs.orglett.8b00590

  日期：2018.4.20

  A highly selective and practical asymmetric Ag(I) catalyst system has been developed for the [3 + 2] cycloaddition reactions between isocyanoacetates and cyclopentenediones. The current Ag(I) catalyst system tolerates moisture and air and readily utilizes class III solvents such as EtOAc and acetone. The development of on demand generation of an active chiral catalyst in the presence of isocyanides

  已开发出一种高度选择性和实用的不对称Ag（I）催化剂体系，用于异氰基乙酸酯和环戊二酮之间的[3 + 2]环加成反应。当前的Ag（I）催化剂体系可耐受水分和空气，并容易利用III类溶剂（如EtOAc和丙酮）。的发展需求代异氰化物的存在下活性手性催化剂的铺平的方式双环吡咯烷的高效制备不对称具有四个手性中心，其中包括80-97％ee的两个四价中心。
• Asymmetric Formal [3+2] Cycloaddition Reaction of Isocyanoesters to 2‐Oxobutenoate Esters by a Multifunctional Chiral Silver Catalyst
  作者：Jin Song、Chang Guo、Peng‐Hao Chen、Jie Yu、Shi‐Wei Luo、Liu‐Zhu Gong

  DOI：10.1002/chem.201100636

  日期：2011.7.4

  Silver‐standard selectivity! The first highly enantioselective formal [3+2] cycloaddition reaction of isocyanoesters with 2‐oxobutenoate esters catalyzed by a chiral silver complex proceeded readily under the catalysis of a multifunctional chiral silver complex in high yields and enantiometric excess (ee) values of up to 98 % (see scheme).

  银标准选择性！多功能手性银配合物的催化下，异氰酸酯与2-氧代丁烯酸酯的第一个高对映选择性的正式[3 + 2]环加成反应在多功能手性银配合物的催化下容易进行，产率高，对映体过量（ee）值高达98 ％（请参阅方案）。
• Regioselective Synthesis of Pyrroles from Alkyne-Isocyanide Click Reactions: An Angle Strain-Induced Bond Migration Approach
  作者：Jimil George、Hun Young Kim、Kyungsoo Oh

  DOI：10.1002/adsc.201601017

  日期：2016.12.7

  direct regioselective synthesis of highly functionalized pyrroles with two different electron‐withdrawing groups has been developed using an angle strain‐induced 1,2‐shift of an electron‐withdrawing group in 2H‐pyrroles. The preferential migration aptitude of an electron‐withdrawing group over alkyl and aryl groups is believed to be the result of the orbital overlap between the internal alkene and the

  利用在2个H吡咯中的吸电子基团的角应变诱导的1,2-位移，开发了具有两个不同的吸电子基团的高度官能化吡咯的直接区域选择性合成方法。吸电子基团优先于烷基和芳基的迁移能力被认为是内部烯烃与吸电子基团之间轨道重叠的结果。新开发的吡咯区域选择性合成具有广泛的底物范围，简单的反应设置和高收率（60-82％），捕获了炔烃-异氰“点击”反应的本质。
• Chiral squaramides catalyzed diastereo- and enantioselective Michael addition of α-substituted isocyanoacetates to N-aryl maleimides
  作者：Mei-Xin Zhao、Fei-Hu Ji、Deng-Ke Wei、Min Shi

  DOI：10.1016/j.tet.2013.09.084

  日期：2013.12

  An efficient diastereo- and enantioselective Michael addition of α-substituted isocyanoacetates to N-aryl maleimides catalyzed by quinine or cyclohexane-1,2-diamine derived squaramide catalysts has been disclosed, affording the corresponding adducts in good yields (up to 99%), high diastereoselectivities (up to >20:1 dr) and good to excellent enantioselectivities (up to 94% ee) under mild conditions

  已经公开了由奎宁或环己烷-1，2-二胺衍生的方酰胺催化剂催化的α-取代的异氰基乙酸酯向N-芳基马来酰亚胺的高效非对映和对映选择性迈克尔加成反应，可提供相应的加合物，收率高（高达99％），非对映选择性高（高达> 20：1 dr），在温和条件下良好至优异的对映选择性（高达94％ee）。