2-氯-1-(1-甲基-1H-咪唑-2-基)乙酮 | 860772-72-1

• 分子结构分类: 有机化合物 - 有机氧化合物
• 中文名称: 2-氯-1-(1-甲基-1H-咪唑-2-基)乙酮
• 英文名称: 2-chloro-1-(1-methyl-1H-imidazole-2-yl)ethanone
• 英文别名: 2-Chloro-1-(1-methyl-1H-imidazol-2-yl)ethanone；2-chloro-1-(1-methylimidazol-2-yl)ethanone
• CAS: 860772-72-1
• 化学式: C₆H₇ClN₂O
• mdl: MFCD16878432
• 分子量: 158.587
• InChiKey: MLIMAEFXKFJJSR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.333
• 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：

  2-氯-1-(1-甲基-1H-咪唑-2-基)乙酮 在 2,6-双[(3aR,8aS)-(+)-8H-茚[1,2-d]恶唑啉-2-基]吡啶 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 氯仿 、 甲苯 、 苯 为溶剂， 生成 3-[2-(1-methyl-1H-imidazol-2-yl)-2-oxoethyl]-2-methylene-6-((triisopropylsilyl)oxy)hexanenitrile
  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：

  N-甲基咪唑 、 氯乙酸叔丁酯 在 正丁基锂 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 2.5h， 以99%的产率得到2-氯-1-(1-甲基-1H-咪唑-2-基)乙酮
  参考文献：
  名称：

  双(恶唑啉基)吡啶-钪(III)三氟甲磺酸盐配合物催化α,β-不饱和2-酰基咪唑的对映选择性Friedel-Crafts烷基化

  摘要：

  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。

  DOI：

  10.1021/ja052433d

文献信息

• 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。
• Asymmetric Catalysis with Substitutionally Labile yet Stereochemically Stable Chiral-at-Metal Iridium(III) Complex
  作者：Haohua Huo、Chen Fu、Klaus Harms、Eric Meggers

  DOI：10.1021/ja4132505

  日期：2014.2.26

  A metal-coordination-based high performance asymmetric catalyst utilizing metal centrochirality as the sole element of chirality is reported. The introduced substitutionally labile chiral-at-metal octahedral iridium(III) complex exclusively bears achiral ligands and effectively catalyzes the enantioselective Friedel-Crafts addition of indoles to α,β-unsaturated 2-acyl imidazoles (19 examples) with

  报道了一种利用金属中心手性作为唯一手性元素的基于金属配位的高性能不对称催化剂。引入的取代不稳定手性金属八面体铱 (III) 配合物仅带有非手性配体，并以高产率（75%）有效催化吲哚与 α,β-不饱和 2-酰基咪唑（19 个实例）的对映选择性弗里德尔-克拉夫茨加成-99%) 和高对映选择性 (90-98% ee) 在低催化剂负载 (0.25-2 mol %) 下。与直觉相反，尽管其置换不稳定，这是与 2-酰基咪唑底物配位所必需的，但金属中心手性在整个催化过程中保持不变。这种新型的活性手性金属配合物可能对各种不对称转化具有很高的价值。
• Direct Access to Highly Enantioenriched α-Branched Acrylonitriles through a One-Pot Sequential Asymmetric Michael Addition/Retro-Dieckmann/Retro-Michael Fragmentation Cascade
  作者：Nicolas Duchemin、Martin Cattoen、Oscar Gayraud、Silvia Anselmi、Bilal Siddiq、Roberto Buccafusca、Marc Daumas、Vincent Ferey、Michael Smietana、Stellios Arseniyadis

  DOI：10.1021/acs.orglett.0c02079

  日期：2020.8.7

  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.
• Catalytic Asymmetric Decarboxylative Michael Addition To Construct an All-Carbon Quaternary Center with 3-Alkenyl-oxindoles
  作者：Yingzheng Ren、Shuhui Lu、Lin He、Zhifei Zhao、Shi-Wu Li

  DOI：10.1021/acs.orglett.2c00411

  日期：2022.4.15

  The first highly enantioselective asymmetric decarboxylative addition of β-keto acids with 3-alkenyl-oxindoles bearing an all-carbon quaternary stereocenter have been developed. The relevant products were acquired in 49–98% yields with 88–98% enantioselectivities in the presence of 0.04–1.0 mol % of chiral rhodium catalyst. The comprehensive practicability of this method was proven in the preparation

  已经开发了第一个高度对映选择性的不对称脱羧加成 β-酮酸与带有全碳四元立体中心的 3-烯基-羟吲哚。在 0.04-1.0 mol% 的手性铑催化剂存在下，相关产物的收率为 49-98%，对映选择性为 88-98%。该方法的综合实用性在关键中间体的制备中得到了验证，该中间体可以很容易地转化为毒扁豆碱和毒扁豆碱的类似物。