methyl 2-isocyano-2-(4-bromophenyl)acetate | 1452588-95-2

• 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-bromophenyl)acetate
• 英文别名: methyl 2-(4-bromophenyl)-2-isocyanoacetate
• CAS: 1452588-95-2
• 化学式: C₁₀H₈BrNO₂
• 分子量: 254.083
• InChiKey: ICGVFFMIKGCRGR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.4
• 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：
  3

反应信息

• 作为反应物：
  描述：

  methyl 2-isocyano-2-(4-bromophenyl)acetate 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-bromophenyl)-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：

  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 methyl 2-isocyano-2-(4-bromophenyl)acetate
  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。
• 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）。
• Cinchona alkaloid thiourea mediated asymmetric Mannich reaction of isocyanoacetates with isatin-derived ketimines and subsequent cyclization: enantioselective synthesis of spirooxindole imidazolines
  作者：Mei-Xin Zhao、Lei Jing、Hao Zhou、Min Shi

  DOI：10.1039/c5ra17075c

  日期：——

  The organocatalyzed asymmetric Mannich reaction of isocyanoacetates with isatin ketimines and subsequent cyclization were developed, leading to spirooxindole imidazolines in high yields and excellent stereoselectivities.

  有机催化的对映选择性Mannich反应，使用异氰基乙酸酯与异喹啉酮亚胺反应，并随后进行环化反应，产率高且立体选择性优异，形成螺环氧吲哚咪唑啉。
• Metal‐free Decarboxylative Annulation of 2‐Aryl‐2‐isocyano‐acetates with Aryldiazonium Salts: General Access to 1,3‐Diaryl‐1,2,4‐triazoles
  作者：Yu‐Ting Tian、Fa‐Guang Zhang、Jing Nie、Chi Wai Cheung、Jun‐An Ma

  DOI：10.1002/adsc.202001016

  日期：2021.1.5

  Isocyanoacetates are versatile substrates for the synthesis of heterocyclic compounds, but the concomitant decarboxylation remains rare. Herein we report a decarboxylative annulation reaction of 2‐aryl‐2‐isocyanoacetates with aryldiazonium salts. This metal‐free, base‐promoted protocol allows for the access to a broad collection of 1,3‐diaryl‐1,2,4‐triazoles, including chiral triazole‐based binaphthalene

  异氰基乙酸酯是用于合成杂环化合物的通用底物，但伴随的脱羧作用仍然很少。在本文中，我们报告了2-芳基-2-异氰基乙酸盐与芳基重氮盐的脱羧环化反应。这种无金属，碱促进的方案允许访问广泛的1,3-二芳基1,2,4-三唑类化合物，包括基于手性三唑的双萘配体，药物模拟物和药物样分子的合成中间体。
• Organocatalyzed asymmetric tandem conjugate addition–protonation of isocyanoacetates to 2-chloroacrylonitrile
  作者：Kun-Ming Yu、Hui-Kai Zhu、Xiao-Li Zhao、Min Shi、Mei-Xin Zhao

  DOI：10.1039/c8ob02833h

  日期：——

  organocatalytic asymmetric tandem conjugate addition–protonation of α-substituted isocyanoacetates to 2-chloroacrylonitrile catalyzed by dihydroquinine-derived thiourea has been investigated, affording the corresponding adducts with two non-adjacent tertiary–quaternary stereocenters in excellent yields (up to 99%) along with good to excellent diastereo- and enantioselectivities (up to 20 : 1 dr, up to 95%

  研究了一种有效的有机催化不对称串联共轭加成反应—由二氢奎宁衍生的硫脲催化α-取代的异氰基乙酸酯质子化成2-氯丙烯腈，并以优异的收率（高达99％）为相应的加合物提供了两个不相邻的叔-四级立体中心。在温和条件下具有良好至优异的非对映选择性和对映选择性（最高20：1 dr，最高95％ee）。该加合物还可以通过合成转化而转化为手性γ-内酰胺。