1-(1-methyl-1H-imidazole-2-yl)-2-(triphenylphosphoranylidene)-ethanone | 860772-73-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: 1-(1-methyl-1H-imidazole-2-yl)-2-(triphenylphosphoranylidene)-ethanone
• 英文别名: 1-(1-methyl-1H-imidazol-2-yl)-2-(triphenylphosphaneylidene)ethan-1-one；1-(1-methyl-1H-imidazol-2-yl)-2-(triphenylphosphoranylidene)-ethanone；1-(1-methyl-1H-imidazole-2-yl)-2-(triphenylphosphoranylidene)ethanone；1-(1-methyl-1H-imidazol-2-yl)-2-(triphenylphosphoranylidene)ethanone
• CAS: 860772-73-2
• 化学式: C₂₄H₂₁N₂OP
• 分子量: 384.417
• InChiKey: MGBDCSFOESTZAO-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  28.0
• 可旋转键数：
  5.0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.04
• 拓扑面积：
  34.89
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  1-(1-methyl-1H-imidazole-2-yl)-2-(triphenylphosphoranylidene)-ethanone 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 、 苯 为溶剂， 生成 3-(cyclohexylmethyl)-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-氯-1-(1-甲基-1H-咪唑-2-基)乙酮 、 三苯基膦 以 甲苯 为溶剂， 以96%的产率得到1-(1-methyl-1H-imidazole-2-yl)-2-(triphenylphosphoranylidene)-ethanone
  参考文献：
  名称：

  具有取代不稳定但立体化学稳定的手性金属铱（III）配合物的不对称催化

  摘要：

  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。

  DOI：

  10.1021/ja4132505

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。
• Asymmetric Synthesis of Hydrocarbazoles Catalyzed by an Octahedral Chiral-at-Rhodium Lewis Acid
  作者：Yong Huang、Liangliang Song、Lei Gong、Eric Meggers

  DOI：10.1002/asia.201500764

  日期：2015.12

  bis‐cyclometalated chiral‐at‐metal rhodium complex catalyzes the Diels–Alder reaction between N‐Boc‐protected 3‐vinylindoles (Boc=tert‐butyloxycarbonyl) and β‐carboxylic ester‐substituted α,β‐unsaturated 2‐acyl imidazoles with good‐to‐excellent regioselectivity (up to 99:1) and excellent diastereoselectivity (>50:1 d.r.) as well as enantioselectivity (92–99 % ee) under optimized conditions. The rhodium catalyst

  双环金属化的手性金属铑配合物催化N -Boc保护的3-乙烯基吲哚（Boc =叔-丁氧基羰基）与β-羧酸酯取代的α，β-不饱和2-酰基咪唑之间的Diels-Alder反应在最佳条件下，区域选择性很好（高达99：1），非对映选择性（> 50：1 dr）和对映选择性（92–99％ee）。铑催化剂起手性路易斯酸的作用，通过两点结合来活化2-酰基咪唑二烯亲和体，并否决了未催化反应的优选区域选择性。
• Enantioselective 2-Alkylation of 3-Substituted Indoles with Dual Chiral Lewis Acid/Hydrogen-Bond-Mediated Catalyst
  作者：Zijun Zhou、Yanjun Li、Lei Gong、Eric Meggers

  DOI：10.1021/acs.orglett.6b03500

  日期：2017.1.6

  hydrogen bond formation. This new bifunctional chiral Lewis acid/hydrogen-bond-mediated catalyst permits the challenging enantioselective 2-alkylation of 3-substituted indoles with α,β-unsaturated 2-acyl imidazoles in up to 99% yield and with up to 98% enantiomeric excess at a catalyst loading of 2 mol %. As an application, the straightforward synthesis of a chiral pyrrolo[1,2-a]indole is demonstrated.

  手性金属双环金属化铱配合物将通过金属配位的亲电子活化与通过氢键形成的亲核活化结合在一起。这种新型的双功能手性路易斯酸/氢键介导的催化剂可实现具有α，β-不饱和2-酰基咪唑的3-取代吲哚的具有挑战性的对映选择性2-烷基化，产率最高可达99％，对映体过量可达98％。催化剂负载量为2摩尔％。作为一种应用，证明了手性吡咯并[1,2- a ]吲哚的直接合成。
• Organocatalyzed Asymmetric Conjugate Addition of Heteroaryl and Aryl Trifluoroborates: a Synthetic Strategy for Discoipyrrole D
  作者：Jiun‐Le Shih、Thien S. Nguyen、Jeremy A. May

  DOI：10.1002/anie.201503528

  日期：2015.8.17

  Bis‐heteroaryl or bis‐aryl stereocenters were formed by an organocatalytic enantioselective conjugate addition using the respective trifluoroborate salts as nucleophiles. Control studies suggested that fluoride dissociation is necessary in the anhydrous conditions. This strategy is applicable to the synthesis of discoipyrrole D, an inhibitor of BR5 fibroblast migration.

  使用相应的三氟硼酸盐作为亲核试剂，通过有机催化对映选择性共轭加成反应形成双-杂芳基或双-芳基立体中心。对照研究表明，在无水条件下氟化物离解是必要的。该策略适用于盘状吡咯D的合成，盘状吡咯D是BR5成纤维细胞迁移的抑制剂。
• 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。