methyl (2Z)-3-{[(dimethylamino)carbonyl]oxy}but-2-enoate | 1416425-79-0

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: methyl (2Z)-3-{[(dimethylamino)carbonyl]oxy}but-2-enoate
• 英文别名: 3-dimethylcarbamoyloxybut-2-enoic acid methyl ester；(Z)-methyl 3-((dimethylcarbamoyl)oxy)but-2-enoate；(Z)-methyl-3-((dimethylcarbamoyl)oxy)but-2-enoate；methyl 3-(dimethylcarbamoyloxy)but-2-enoate；methyl (Z)-3-(dimethylcarbamoyloxy)but-2-enoate
• CAS: 1416425-79-0
• 化学式: C₈H₁₃NO₄
• 分子量: 187.196
• InChiKey: LPRJUHKFBMHGBW-WAYWQWQTSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  55.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  乙酰乙酸甲酯 、 N,N-二甲基甲酰胺 在 叔丁基过氧化氢 、 copper(l) chloride 作用下， 以 水 为溶剂， 反应 0.5h， 以85%的产率得到methyl (2Z)-3-{[(dimethylamino)carbonyl]oxy}but-2-enoate
  参考文献：
  名称：

  甲酰胺直接 CH 键活化合成氨基甲酸酯

  摘要：

  铜催化甲酰胺与β-酮酯和2-羰基取代酚的氧化偶联反应通过甲酰胺的直接C-H键活化成功进行。在温和的反应条件下以高立体选择性形成相应的氨基甲酸酯。该协议已成功应用于三种新型卤代氨基甲酸酯和甲萘威杀虫剂衍生物的合成。我们的结果建议使用 6.0 当量。TBHP 对于此类反应至关重要。

  DOI：

  10.1002/ejoc.201201160

文献信息

• Synthesis of Carbamates by Direct C-H Bond Activation of Formamides
  作者：Balaji D. Barve、Yang-Chang Wu、Mohamed El-Shazly、Da-Wei Chuang、Yu-Ming Chung、Yi-Hong Tsai、Shou-Fang Wu、Michal Korinek、Ying-Chi Du、Chi-Ting Hsieh、Jeh-Jeng Wang、Fang-Rong Chang

  DOI：10.1002/ejoc.201201160

  日期：2012.12

  catalysed oxidative coupling reaction of formamides with β-keto esters and 2-carbonyl-substituted phenols successfully proceeded through direct C–H bond activation of formamides. The corresponding carbamates were formed with high stereoselectivity under mild reaction conditions. This protocol was successfully applied to the synthesis of three novel halogenated carbamates and a carbaryl insecticide derivative

  铜催化甲酰胺与β-酮酯和2-羰基取代酚的氧化偶联反应通过甲酰胺的直接C-H键活化成功进行。在温和的反应条件下以高立体选择性形成相应的氨基甲酸酯。该协议已成功应用于三种新型卤代氨基甲酸酯和甲萘威杀虫剂衍生物的合成。我们的结果建议使用 6.0 当量。TBHP 对于此类反应至关重要。
• Copper-Catalyzed Oxidative CO Coupling by Direct CH Bond Activation of Formamides: Synthesis of Enol Carbamates and 2-Carbonyl-Substituted Phenol Carbamates
  作者：G. Sathish Kumar、C. Uma Maheswari、R. Arun Kumar、M. Lakshmi Kantam、K. Rajender Reddy

  DOI：10.1002/anie.201105020

  日期：2011.12.2

  Formamide CH bond activation has been achieved under oxidative conditions, using a copper catalyst and tert‐butyl hydroperoxide (TBHP) as the external oxidant (see scheme). This oxidative coupling of a range of dialkyl formamides provides an easy, phosgene‐free route for the selective synthesis of Z‐enol carbamates and 2‐carbonyl‐substituted phenol carbamates in high yields.

  使用铜催化剂和叔丁基氢过氧化物（TBHP）作为外部氧化剂，可以在氧化条件下实现甲酰胺CH键的活化（参见方案）。多种二烷基甲酰胺的这种氧化偶联为高产率地选择性合成Z-烯醇氨基甲酸酯和2-羰基取代的苯甲酸氨基甲酸酯提供了一种简单，无光气的途径。
• Anchoring of a Copper(II)–Schiff Base Complex onto Silica-Coated Ferrite Nanoparticles: A Magnetically Separable Catalyst for Oxidative C–O Coupling by Direct C(sp2)–H and C(sp3)–H Bond Activation
  作者：Rashid Ghanbaripour、Marjaneh Samadizadeh、Golnaz Honarpisheh、Majid Abdolmohammadi

  DOI：10.1055/s-0035-1560067

  日期：——

  A novel catalyst consisting of a Schiff base-copper complex on surface-modified silica-coated ferrite nanoparticles was been prepared and used for oxidative C-O cross-coupling reactions of 1,3-dicarbonyl compounds with formamides for the synthesis of enol carbamates. The new catalyst has also been used for esterification of alkylbenzenes with cyclic ethers.
• Copper nanoparticles on charcoal: an effective nanocatalyst for the synthesis of enol carbamates and amides via an oxidative coupling route
  作者：Dariush Saberi、Sakineh Mansoori、Esmali Ghaderi、Khodabakhsh Niknam

  DOI：10.1016/j.tetlet.2015.11.072

  日期：2016.1

  The catalytic activity of copper nanoparticles on charcoal (Cu/C) was investigated as an environmentally friendly heterogeneous catalyst for the synthesis of enol carbamates and amides via the oxidative coupling of N,N-dialkyl formamides with 1,3-dicarbonyl compounds and aromatic aldehydes with amine hydrochloride salts, respectively. Various enol carbamates and amides were synthesized in moderate to good yields using this method. Moreover, the catalyst could be recovered and subsequently reused in further reactions. (C) 2015 Elsevier Ltd. All rights reserved.
• CuO nanoparticles supported on α-Fe2O3-modified CNTs: a magnetically separable catalyst for oxidative C–O coupling of formamides with 1,3-dicarbonyl compounds
  作者：Dariush Saberi、Akbar Heydari

  DOI：10.1016/j.tetlet.2013.05.113

  日期：2013.8

  Oxidative coupling of formamides with 1,3-dicarbonyl compounds to prepare enol carbamates was effected in the presence of CuO nanoparticles supported on alpha-Fe2O3-modified carbon nanotubes (CNTs@alpha-Fe2O3@CuO) as an environmentally friendly heterogeneous catalyst. The simple preparation, and the ability to be recycled and magnetically separated are salient features of this catalytic system. (C) 2013 Elsevier Ltd. All rights reserved.