methyl 2-isocyano-2-(4-methoxyphenyl)acetate | 853945-70-7

• 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
• 英文名称: methyl 2-isocyano-2-(4-methoxyphenyl)acetate
• CAS: 853945-70-7
• 化学式: C₁₁H₁₁NO₃
• 分子量: 205.213
• InChiKey: ONFVGALCDQMNSE-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 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：
  39.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  methyl 2-isocyano-2-(4-methoxyphenyl)acetate 在 氢氧化钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 20.17h， 生成
  参考文献：
  名称：

  Mild Oxidative One-Carbon Homologation of Aldehyde to Amide

  摘要：

  One-carbon homologation of aldehyde into amide is realized in one-pot by its reaction with potassium alpha-p-methoxyphenyl-alpha-isocyano acetic acid (1c) and hydrochloride salt of dimethylamine (3a) in toluene at room temperature followed by acidic workup. In this multicomponent reaction, 1c served as donor of the CONH2 function to aldehyde, while the dimethylamine acted as a shuttle molecule to initiate/terminate the sequence and to mediate the internal redox process of one of the three-component adducts. Ready accessibility, nominal cost of the reagents, and mild conditions are attractive features of the present method.

  DOI：

  10.1021/ja0511220
• 作为产物：
  描述：

  氨基(3-氯-4-甲氧基苯基)乙酸甲酯盐酸盐 在 二异丙胺 、 三氯氧磷 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 13.0h， 生成 methyl 2-isocyano-2-(4-methoxyphenyl)acetate
  参考文献：
  名称：

  Mild Oxidative One-Carbon Homologation of Aldehyde to Amide

  摘要：

  One-carbon homologation of aldehyde into amide is realized in one-pot by its reaction with potassium alpha-p-methoxyphenyl-alpha-isocyano acetic acid (1c) and hydrochloride salt of dimethylamine (3a) in toluene at room temperature followed by acidic workup. In this multicomponent reaction, 1c served as donor of the CONH2 function to aldehyde, while the dimethylamine acted as a shuttle molecule to initiate/terminate the sequence and to mediate the internal redox process of one of the three-component adducts. Ready accessibility, nominal cost of the reagents, and mild conditions are attractive features of the present method.

  DOI：

  10.1021/ja0511220

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。
• Catalytic Asymmetric [3 + 2] Cycloaddition Reaction between Aurones and Isocyanoacetates: Access to Spiropyrrolines via Silver Catalysis
  作者：Zhi-Peng Wang、Sichuan Xiang、Pan-Lin Shao、Yun He

  DOI：10.1021/acs.joc.8b01622

  日期：2018.9.21

  The first enantioselective formal [3 + 2] cycloaddition of aurone analogues with isocyanoacetates was developed via chiral Ag-complex catalysis. A variety of optically enriched spiro-1-pyrrolines were obtained in excellent yields, diastero- and enantioselectivities (up to 99% yield, >20:1 dr, >99% ee). This synthetic approach represents an extremely simple, efficient, and atom-economical method for

  通过手性Ag络合物催化，开发了具有异氰基乙酸酯的金酮类似物的第一个对映选择性的正式[3 + 2]环加成反应。以优异的收率，非对映选择性和对映选择性（高达99％的收率，> 20：1 dr，> 99％ee的收率）获得了各种光学富集的螺-1-吡咯啉。这种合成方法代表了螺-1-吡咯啉合成的一种极其简单，有效且经济的方法。