1-(3,4-Dichloro-phenyl)-2-(triphenyl-λ⁵-phosphanylidene)-ethanone | 56893-10-8

• 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-(3,4-Dichloro-phenyl)-2-(triphenyl-λ⁵-phosphanylidene)-ethanone
• 英文别名: 1-(3,4-Dichlorophenyl)-2-(triphenyl-lambda5-phosphanylidene)ethanone；1-(3,4-dichlorophenyl)-2-(triphenyl-λ5-phosphanylidene)ethanone
• CAS: 56893-10-8
• 化学式: C₂₆H₁₉Cl₂OP
• 分子量: 449.316
• InChiKey: IFCTYLDTQXMKQY-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  7.2
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  1-(3,4-Dichloro-phenyl)-2-(triphenyl-λ⁵-phosphanylidene)-ethanone 在 1,10-菲罗啉 、 caesium carbonate 、 三乙胺 、 copper(I) bromide 作用下， 以 正己烷 、 二氯甲烷 、 二甲基亚砜 为溶剂， 反应 12.17h， 生成 (2-(but-1-en-2-yl)-5-(tert-butyl)benzofuran-3-yl)(3,4-dichlorophenyl)methanone
  参考文献：
  名称：

  Synthesis of 2-Vinylbenzofurans via the Copper-Catalyzed Multicomponent Reactions Involving an Oxa-Michael/Arylation/Vinylation Cascade

  摘要：

  2-vinylbenzofurans have been synthesized via the copper catalyzed. one-pot, three component reactions of o-iodophenols in situ generated allenes, and dichloromethane Cascade transformation of oxa-Michael addition C-arylation, and sp(3)C-H/sp(3)C-Cl conversion-based vinylation has been involved in realizing the construction of this 2-vinylbenzofuran framework.

  DOI：

  10.1021/ol502506g
• 作为产物：
  描述：

  2-溴-3',4'-二氯苯乙酮 在 sodium hydroxide 作用下， 以 四氢呋喃 、 二氯甲烷 、 水 为溶剂， 反应 4.0h， 生成 1-(3,4-Dichloro-phenyl)-2-(triphenyl-λ⁵-phosphanylidene)-ethanone
  参考文献：
  名称：

  硅胶促进的由色胺和γ-氯-α，β-不饱和酮合成多取代螺亚胺

  摘要：

  在这里，我们报道了由一系列具有γ-氯-α，β-不饱和酮的色胺胺衍生物一锅法合成的多取代螺环吲哚胺。反应顺序包括碱诱导的缩合反应和硅胶促进的分子内迈克尔加成反应。目标分子的产率高达90％，非对映选择性高达> 20：1 。

  DOI：

  10.1016/j.tet.2020.131765

文献信息

• Aerobic Oxidative Dehydrogenation of Ketones to 1,4-Enediones
  作者：Bao-Yin Zhao、Xing-Long Zhang、Rui-Li Guo、Meng-Yue Wang、Ya-Ru Gao、Yong-Qiang Wang

  DOI：10.1021/acs.orglett.0c04174

  日期：2021.2.19

  An efficient and unprecedented strategy for the synthesis of 1,4-enediones from saturated ketones has been developed via palladium-catalyzed oxidative dehydrogenation. The protocol employs molecular oxygen as the sole oxidant and represents an atom- and step-economic process. The approach showed broad substrate scope, good functional group tolerance, and complete E-stereoselectivity. The reaction mechanism

  通过钯催化的氧化脱氢，已经开发出一种有效且空前的从饱和酮合成1,4-二烯酮的策略。该协议采用分子氧作为唯一的氧化剂，代表了原子经济和逐步经济的过程。该方法显示出广泛的底物范围，良好的官能团耐受性和完全的E-立体选择性。通过氘标记实验和中间实验研究了反应机理。
• A Highly Regio- and Stereoselective Cascade Annulation of Enals and Benzodi(enone)s Catalyzed by N-Heterocyclic Carbenes
  作者：Xinqiang Fang、Kun Jiang、Chong Xing、Lin Hao、Yonggui Robin Chi

  DOI：10.1002/anie.201007144

  日期：2011.2.18

  Three stereogenic centers in a row: The unconventional activation of enal compounds mediated by an N‐heterocyclic carbene (NHC) has generated three consecutive reactive carbon centers that undergo highly regio‐ and stereoselective annulations with di(enone)s to generate benzotricyclic products containing multiple stereogenic centers (see scheme).

  连续三个立体生成中心：由N杂环卡宾（NHC）介导的烯类化合物的非常规活化产生了三个连续的活性碳中心，这些中心经历了对二（烯酮）的高度区域和立体选择性环化反应，从而生成包含多个立体定位中心（请参阅方案）。
• Rh-Catalyzed diastereoselective desymmetrization of enone tethered-cyclohexadienones <i>via</i> tandem arylative cyclization
  作者：Sandip B. Jadhav、Satish B. Thopate、Jagadeesh Babu Nanubolu、Rambabu Chegondi

  DOI：10.1039/c8ob02284d

  日期：——

  rhodium-catalyzed arylative cyclization of enone tethered-cyclohexadienones has been developed with high efficiency, thus providing cis-fused bicyclic enones in good yields and with excellent diastereoselectivities. Furthermore, this mild transformation has a broad range of substrate scope and excellent functional group tolerance. In addition, bicyclic products have an enone functionality, which can be

  烯酮系环己二酮的铑催化的芳基环化反应已得到高效开发，从而以高收率和极好的非对映选择性提供了顺式稠合双环烯酮。此外，这种温和的转化具有广泛的底物范围和优异的官能团耐受性。此外，双环产物具有烯酮官能团，可以作为进一步转化的合成有价值的处理方法。
• Phosphine-Catalyzed [3+2] Annulation of β-Sulfonamido-Substituted Enones with Sulfamate-Derived Cyclic Imines
  作者：Wangyu Shi、Leijie Zhou、Biming Mao、Qijun Wang、Chang Wang、Cheng Zhang、Xuefeng Li、Yumei Xiao、Hongchao Guo

  DOI：10.1021/acs.joc.8b02515

  日期：2019.1.18

  Phosphine-catalyzed [3+2] annulation of β-sulfonamido-substituted enones and sulfamate-derived cyclic imines has been developed, giving a series of imidazoline derivatives in moderate to excellent yields with good to excellent diastereoselectivities. A scale-up reaction worked well under mild reaction conditions. A possible mechanism was proposed on the basis of the results obtained.

  已经开发了膦催化的β-磺酰胺基取代的烯酮和氨基磺酸衍生的环状亚胺的[3 + 2]环化反应，从而以中等至优异的收率提供了一系列咪唑啉衍生物，并具有良好或优异的非对映选择性。放大反应在温和的反应条件下效果很好。根据获得的结果，提出了一种可能的机制。
• Phosphine-Catalyzed (4 + 2) Annulation of δ-Sulfonamido-Substituted Enones with 1,1-Dicyanoalkenes: Synthesis of Piperidine Derivatives
  作者：Min Liu、Leijie Zhou、Wangyu Shi、Yimin Hu、Jianning Liao、Zeqing Duan、Wei Wang、Yongjun Wu、Bing Zheng、Hongchao Guo

  DOI：10.1021/acs.orglett.1c02557

  日期：2021.10.15

  The δ-sulfonamido-substituted enones were employed as phosphine acceptor in phosphine-catalyzed (4 + 2) annulation of 1,1-dicyanoalkenes. They served as a four-membered synthon to react with 1,1-dicyanoalkenes under mild reaction conditions, producing piperidine derivatives in moderate to excellent yields with good to excellent diastereoselectivities.

  δ-磺酰氨基取代的烯酮在膦催化的 1,1-二氰基烯烃 (4 + 2) 环化中用作膦受体。它们作为四元合成子在温和的反应条件下与 1,1-二氰基烯烃反应，以中等至优异的收率产生哌啶衍生物，并具有良好至优异的非对映选择性。