(E)-1-(1-methyl-1H-imidazol-2-yl)pent-2-en-1-one | 860772-39-0

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (E)-1-(1-methyl-1H-imidazol-2-yl)pent-2-en-1-one
• 英文别名: (E)-1-(1-methylimidazol-2-yl)pent-2-en-1-one
• CAS: 860772-39-0
• 化学式: C₉H₁₂N₂O
• 分子量: 164.207
• InChiKey: NENRESQHFIJNCF-SNAWJCMRSA-N

物化性质

• 沸点：
  304.5±25.0 °C(Predicted)
• 密度：
  1.02±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.3
• 重原子数：
  12
• 可旋转键数：
  3
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  34.9
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-1-(1-methyl-1H-imidazol-2-yl)pent-2-en-1-one 、 4-氰基-3-四氢噻吩酮 在 2,6-双[(3aR,8aS)-(+)-8H-茚[1,2-d]恶唑啉-2-基]吡啶 、 scandium tris(trifluoromethanesulfonate) 、 四丁基氢氧化铵 作用下， 以 氯仿 、 甲醇 为溶剂， 以60%的产率得到3-ethyl-5-(1-methyl-1H-imidazol-2-yl)-2-methylene-5-oxopentanenitrile
  参考文献：
  名称：

  Direct Access to Highly Enantioenriched α-Branched Acrylonitriles through a One-Pot Sequential Asymmetric Michael Addition/Retro-Dieckmann/Retro-Michael Fragmentation Cascade

  摘要：

  A highly enantioselective synthesis of alpha-branched acrylonitriles is reported featuring a one-pot sequential asymmetric Michael addition/retro-Dieckmann/retro-Michael fragmentation cascade. The method, which relies on a solid, bench-stable, and commercially available acrylonitrile surrogate, is practical, scalable, and highly versatile and provides a direct access to a wide range of enantioenriched nitrite-containing building blocks. Most importantly, the method offers a new tool to incorporate an acrylonitrile moiety in an asymmetric fashion.

  DOI：

  10.1021/acs.orglett.0c02079
• 作为产物：
  描述：

  2-戊醛 在 manganese(IV) oxide 、 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 9.33h， 生成 (E)-1-(1-methyl-1H-imidazol-2-yl)pent-2-en-1-one
  参考文献：
  名称：

  Direct Access to Highly Enantioenriched α-Branched Acrylonitriles through a One-Pot Sequential Asymmetric Michael Addition/Retro-Dieckmann/Retro-Michael Fragmentation Cascade

  摘要：

  A highly enantioselective synthesis of alpha-branched acrylonitriles is reported featuring a one-pot sequential asymmetric Michael addition/retro-Dieckmann/retro-Michael fragmentation cascade. The method, which relies on a solid, bench-stable, and commercially available acrylonitrile surrogate, is practical, scalable, and highly versatile and provides a direct access to a wide range of enantioenriched nitrite-containing building blocks. Most importantly, the method offers a new tool to incorporate an acrylonitrile moiety in an asymmetric fashion.

  DOI：

  10.1021/acs.orglett.0c02079

文献信息

• Catalytic, Enantioselective Addition of Alkyl Radicals to Alkenes via Visible-Light-Activated Photoredox Catalysis with a Chiral Rhodium Complex
  作者：Haohua Huo、Klaus Harms、Eric Meggers

  DOI：10.1021/jacs.6b03399

  日期：2016.6.8

  An efficient enantioselective addition of alkyl radicals, oxidatively generated from organotrifluoroborates, to acceptor-substituted alkenes is catalyzed by a bis-cyclometalated rhodium catalyst (4 mol %) under photoredox conditions. The practical method provides yields up to 97% with excellent enantioselectivities up to 99% ee and can be classified as a redox neutral, electron-transfer-catalyzed reaction

  在光氧化还原条件下，由双环金属化铑催化剂（4 mol%）催化从有机三氟硼酸盐氧化生成的烷基自由基与受体取代的烯烃的有效对映选择性加成。该实用方法的产率高达 97%，对映选择性高达 99% ee，可归类为氧化还原中性、电子转移催化反应。
• DNA‐Based Asymmetric Inverse Electron‐Demand Hetero‐Diels–Alder
  作者：Justine Mansot、Jimmy Lauberteaux、Aurélien Lebrun、Marc Mauduit、Jean‐Jacques Vasseur、Renata Marcia de Figueiredo、Stellios Arseniyadis、Jean‐Marc Campagne、Michael Smietana

  DOI：10.1002/chem.202000516

  日期：2020.3.18

  yields (up to 99 %) and excellent diastereo- (up to >99:1 dr) and enantioselectivities (up to 95 % ee) using a low catalyst loading. Most importantly, these results show that the concept of DNA-based asymmetric catalysis can be expanded to new synthetic transformations offering an efficient, sustainable, and highly selective tool for the construction of chiral building blocks.

  尽管人工环化酶在化学合成中具有广阔的前景，但这项工作提出了在二氢呋喃和各种α，β-不饱和酰基咪唑之间进行DNA催化的电子反电子异Diels-Alder（IEDHDA）的第一个例子。所得的含有三个连续的立体异构中心的稠合双环O，O-乙缩醛以高收率（高达99％）和优异的非对映异构体（高达> 99：1 dr）和对映选择性（高达95％ee）获得，且收率低。催化剂负载量。最重要的是，这些结果表明，基于DNA的不对称催化的概念可以扩展到新的合成转化过程，从而为构建手性构件提供了有效，可持续和高度选择性的工具。
• Copper-Catalyzed Conjugate Additions of Alkylboranes to Imidazolyl α,β-Unsaturated Ketones: Formal Reductive Conjugate Addition of Terminal Alkenes
  作者：Hirohisa Ohmiya、Mika Yoshida、Masaya Sawamura

  DOI：10.1021/ol102819k

  日期：2011.2.4

  Conjugate addition of alkylboron compounds (alkyl-9-BBN) to imidazol-2-yl α,β-unsaturated ketones proceeded in the presence of a catalytic amount (10 mol %) of CuCl, 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes), and t-BuOK. The alkylboranes are available through alkene hydroboration, and thus the overall process represents a reductive conjugate addition of alkenes to enone derivatives. A

  在催化量（10 mol％）的CuCl，1,3-双（2,4， 6-三甲基苯基）咪唑-2-亚烷基（IMes）和t- BuOK。烷基硼烷可通过烯烃加氢硼化获得，因此整个过程代表了烯烃与烯酮衍生物的还原共轭加成。在烯烃和α，β-不饱和酮中都可以容忍多种官能团。2-酰基咪唑部分可以容易地转化为相应的羧酸，酯和酰胺衍生物。
• Highly Efficient Cyclic Dinucleotide Based Artificial Metalloribozymes for Enantioselective Friedel–Crafts Reactions in Water
  作者：Changhao Wang、Min Hao、Qianqian Qi、Jingshuang Dang、Xingchen Dong、Shuting Lv、Ling Xiong、Huanhuan Gao、Guoqing Jia、Yashao Chen、Jörg S. Hartig、Can Li

  DOI：10.1002/anie.201912962

  日期：2020.2.24

  construct artificial metalloenzymes (ArMs) for enantioselective catalysis. DNA-based ArMs containing duplex and G-quadruplex scaffolds have been widely investigated, yet RNA-based ArMs are scarce. Here we report that a cyclic dinucleotide of c-di-AMP and Cu2+ ions assemble into an artificial metalloribozyme (c-di-AMP⋅Cu2+ ) that enables catalysis of enantioselective Friedel-Crafts reactions in aqueous

  核酸的各种二级结构正以吸引人的手性支架的形式出现，以构建用于对映选择性催化的人工金属酶（ArM）。包含双链体和G-四链体支架的基于DNA的ArM已被广泛研究，但基于RNA的ArM却很少。在这里，我们报道c-di-AMP和Cu2 +离子的环状二核苷酸组装成人工金属核酶（c-di-AMP⋅Cu2+），该催化金属能够在水介质中以高反应性和出色的对映选择性进行催化对映选择性Friedel-Crafts反应。到97％ee。与Cu2 +离子相比，c-di-AMP⋅Cu2+的组装产生了20倍的速率加速。基于各种生物物理技术和密度函数理论（DFT）计算，
• Enantioselective Friedel−Crafts Alkylations of α,β-Unsaturated 2-Acyl Imidazoles Catalyzed by Bis(oxazolinyl)pyridine−Scandium(III) Triflate Complexes
  作者：David A. Evans、Keith R. Fandrick、Hyun-Ji Song

  DOI：10.1021/ja052433d

  日期：2005.6.1

  An enantioselective Friedel−Crafts alkylation with α,β-unsaturated 2-acyl imidazoles and electron-rich aromatic nucleophiles catalyzed by bis(oxazolinyl)pyridine−scandium(III) triflate complexes has been accomplished. These α,β-unsaturated 2-acyl imidazoles are effective electrophiles for the Friedel−Crafts reaction. The resulting adduct 2-acyl imidazole is easily converted to amides, esters, carboxylic

  已经完成了由双（恶唑啉基）吡啶-钪（III）三氟甲磺酸盐配合物催化的α，β-不饱和2-酰基咪唑和富电子芳香亲核试剂的对映选择性Friedel-Crafts烷基化反应。这些 α,β-不饱和 2-酰基咪唑是 Friedel-Crafts 反应的有效亲电试剂。通过甲基化和随后的咪唑残基置换，所得加合物 2-酰基咪唑很容易转化为酰胺、酯、羧酸、酮和醛。