2-(2,2-difluorovinyl)thiophene | 1432484-54-2

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 杂芳族化合物
• 英文名称: 2-(2,2-difluorovinyl)thiophene
• 英文别名: Thiophene, 2-(2,2-difluoroethenyl)-；2-(2,2-difluoroethenyl)thiophene
• CAS: 1432484-54-2
• 化学式: C₆H₄F₂S
• 分子量: 146.161
• InChiKey: LBOZUXPQVXRGCB-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  28.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(2,2-difluorovinyl)thiophene 在 cesium fluoride 作用下， 以 甲醇 、 正己烷 、 二甲基亚砜 、 甲苯 为溶剂， 20.0~30.0 ℃ 、2.03 MPa 条件下， 反应 19.0h， 生成 methyl 3,3,3-trifluoro-2-(thiophen-2-yl)propanoate
  参考文献：
  名称：

  宝石-二氟烯烃的氟羧化反应有效合成α-三氟甲基羧酸和酯

  摘要：

  通过宝石-二氟烯烃，氟化铯和二氧化碳之间的多组分偶联反应，可以轻松地合成α-三氟甲基羧酸和酯。产品的产量中等至极佳，并且通过制备流行的非甾体抗炎药（NSAID）的三氟甲基化形式证明了该方法的合成效用。

  DOI：

  10.1002/anie.201902779
• 作为产物：
  描述：

  2-噻吩甲醛 、 氟磺酰基二氟乙酸甲酯 在 三苯基膦 、 potassium iodide 作用下， 以 乙腈 为溶剂， 反应 4.0h， 以70%的产率得到2-(2,2-difluorovinyl)thiophene
  参考文献：
  名称：

  The use of methyl 2,2-difluoro-2-(fluorosulfonyl)acetate as the difluorocarbene source to generate an in situ source of difluoromethylene triphenylphosphonium ylide

  摘要：

  Under moderate conditions in the presence of a demethylating reagent, such as iodide, methyl 2,2,-difluoro-2-(fluorosulfonyl)acetate (MDFA) releases difluorocarbene, which in the presence of triphenylphosphine forms difluoromethylene triphenylphosphonium ylide. When the process is carried out also in the presence of aldehydes or activated ketones, the ensuing in situ Wittig-type reaction of the ylide with the carbonyl reactants produces 1,1-difluoroalkenes in good yield. Density Functional Theory calculations were used to provide new estimates of the energies and structures of singlet and triplet states of CH2:, CHF:, and CF2: carbenes, as well as those of their respective triphenylphosphonium ylides. (C) 2013 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.jfluchem.2013.02.026

文献信息

• Organocatalytic Nucleophilic Substitution Reaction of <i>gem</i>-Difluoroalkenes with Ketene Silyl Acetals
  作者：Azusa Kondoh、Kazumi Koda、Masahiro Terada

  DOI：10.1021/acs.orglett.9b00566

  日期：2019.4.5

  An organocatalytic nucleophilic substitution reaction of gem-difluoroalkenes with ketene silyl acetals was developed. Phosphazene P4-tBu effectively catalyzed the reaction under mild conditions to provide monofluoroalkenes possessing an alkoxycarbonylmethyl group in high yields with high Z selectivities.

  开发了宝石-二氟烯烃与乙烯酮甲硅烷基缩醛的有机催化亲核取代反应。磷腈P4- t Bu在温和条件下有效催化了该反应，以高收率和高Z选择性提供了具有烷氧羰基甲基的一氟烯烃。
• Sterically Controlled Cu-Catalyzed or Transition-Metal-Free Cross-Coupling of <i>gem</i>-Difluoroalkenes with Tertiary, Secondary, and Primary Alkyl Grignard Reagents
  作者：Wenpeng Dai、Hongyan Shi、Xianghu Zhao、Song Cao

  DOI：10.1021/acs.orglett.6b02026

  日期：2016.9.2

  transition-metal-free cross-coupling of gem-difluoroalkenes with tertiary, secondary, and primary alkyl Grignard reagents has been developed. Remarkably, the tertiary and secondary alkylation of gem-difluoroalkenes proceeded very smoothly in the presence of 25 mol % of CuCN or under transition-metal-free conditions, affording the tertiary and secondary alkyl-substituted fluoroalkenes in good to excellent yields with

  已经开发出一种健壮的铜催化或无过渡金属的宝石-二氟烯烃与叔，仲和伯烷基格氏试剂的交叉偶联。值得注意的是，在25 mol％的CuCN存在下或在无过渡金属的条件下，宝石-二氟烯烃的叔和仲烷基化反应进行得非常顺利，从而以良好的收率和优异的Z立体选择性提供了叔或仲烷基取代的氟代烯烃。 。
• Copper-Catalyzed Coupling Cyclization of <i>gem</i>-Difluoroalkenes with Activated Methylene Carbonyl Compounds: Facile Domino Access to Polysubstituted Furans
  作者：Xuxue Zhang、Wenpeng Dai、Wei Wu、Song Cao

  DOI：10.1021/acs.orglett.5b01123

  日期：2015.6.5

  A novel and efficient CuI-catalyzed synthesis of 2,3,5-trisubstituted furans was developed via coupling cyclization of gem-difluoroalkenes with active methylene carbonyl compounds such as 1,3-dicarbonyl compounds, acetoacetonitrile, and phenylsulfonylacetone with the assistance of a base. Commercial availability of substrates or reagents, good to high isolated yields, and excellent functional group

  通过宝石-二氟烯烃与活性亚甲基羰基化合物（例如1,3-二羰基化合物，乙酰乙腈和苯磺酰丙酮）的偶联环化，开发了新颖，高效的CuI催化的2,3,5-三取代呋喃合成方法。底物或试剂的商业可得性，良好或较高的分离产率以及出色的官能团相容性，使这种转化成为合成各种呋喃的有力工具。提出了一种可能的机制，涉及到烯丙基酮。
• Synthesis of Exocyclic Trisubstituted Alkenes <i>via</i> Nickel‐ Catalyzed Kumada‐Type Cross‐Coupling Reaction of <i>gem</i> ‐ Difluoroalkenes with Di‐Grignard Reagents
  作者：Wenpeng Dai、Xuxue Zhang、Juan Zhang、Yingyin Lin、Song Cao

  DOI：10.1002/adsc.201500889

  日期：2016.1.21

  A practical, nickel‐catalyzed Kumada‐type double cross‐coupling reaction of gem‐difluoroalkenes with 1,4‐ or 1,5‐di‐Grignard reagents was developed. The reaction proceeded efficiently at room temperature and a variety of cyclization products, arylmethylenecyclopentanes and arylmethylenecyclohexanes, were obtained in high to excellent yields, respectively.

  开发了一种实用的镍催化的宝石二氟烯烃与1,4或1,5-二格里雅试剂的Kumada型双交叉偶联反应。该反应在室温下有效地进行，并且分别以高至优异的收率获得了各种环化产物，芳基亚甲基环戊烷和芳基亚甲基环己烷。
• Synthesis of Alkyl Aryl(heteroaryl)acetates from <i>N</i>-Oxides, 1,1-Difluorostyrenes, and Alcohols
  作者：Rafał Loska、Katarzyna Szachowicz、Dorota Szydlik

  DOI：10.1021/ol402735m

  日期：2013.11.15

  anes are formed from imidazole or thiazole N-oxide, 1,1-difluorostyrene, and an alcohol, amine, or water in a three-component reaction, which probably occurs via 1,3-dipolar cycloaddition. The whole process is a novel method for functionalization of a heterocyclic ring in a position originally occupied by hydrogen. Preliminary experiments show that it occurs for 6-membered N-oxides as well.

  芳基（杂芳基）乙酸或芳基（杂芳基）甲烷的衍生物是由咪唑或噻唑N-氧化物，1，1-二氟苯乙烯和醇，胺或水以三组分反应形成的，很可能是通过1 ，3-偶极环加成。整个过程是一种用于在最初被氢占据的位置上杂环官能化的新颖方法。初步实验表明，它也在6元N-氧化物中发生。