1,1,1-trifluoronon-3-en-2-one

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1,1,1-trifluoronon-3-en-2-one
• 英文别名: 1,1,1-Trifluoronon-3-en-2-one
• 化学式: C₉H₁₃F₃O
• 分子量: 194.197
• InChiKey: PKOIVFBXNKIXQA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.9
• 重原子数：
  13
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.67
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  苯乙酸 、 1,1,1-trifluoronon-3-en-2-one 在 lithium aluminium tetrahydride 、 三甲基乙酰氯 、 N,N-二异丙基乙胺 作用下， 以 四氢呋喃 为溶剂， 反应 16.0h， 生成
  参考文献：
  名称：

  Isothiourea-mediated asymmetric Michael-lactonisation of trifluoromethylenones: a synthetic and mechanistic study

  摘要：

  HBTM-2.1在有庚酰氯存在的情况下，促进了芳基乙酸和三氟甲烯酮的催化不对称分子间迈克尔-内酯化反应，生成高二者立体选择性和对映选择性的C(6)-三氟甲基二氢吡喃酮（达到95 : 5的dr和>99% ee），这些产物可以方便地转化为含有三氟甲基手性基团的多样合成构件。动力学研究表明，反应对原位生成的混合酸酐和催化剂浓度均为一级反应，同时在使用α,α-二氘基4-氟苯乙酸的实验中观察到了主要的动力学同位素效应，这与中间体酰基异硫尿阳离子的去质子化作为速率限制步骤一致。

  DOI：

  10.1039/c3sc51791h

文献信息

• Quinidine‐Catalysed Enantioselective Synthesis of 6‐ and 4‐Trifluoromethyl‐Substituted Dihydropyrans
  作者：Kevin Kasten、David B. Cordes、Alexandra M. Z. Slawin、Andrew D. Smith

  DOI：10.1002/ejoc.201600583

  日期：2016.7

  The authors thank the Royal Society for a University Research Fellowship (ADS) and the European Research Council under the European Union’s Seventh Framework Programme (FP7/2007-2013), ERC Grant Agreement No. 279850 (KK), the authors also thank the EPSRC UK National Mass Spectrometry Facility at Swansea University.

  作者感谢皇家学会提供的大学研究奖学金 (ADS) 和欧盟第七框架计划 (FP7/2007-2013) 下的欧洲研究理事会，ERC 赠款协议编号 279850 (KK)，作者还感谢 EPSRC斯旺西大学的英国国家质谱设施。
• Highly efficient, asymmetric, and organocatalyst-based Henry reactions between α,β-unsaturated trifluoromethyl ketone and nitromethane
  作者：Ryo Tsuyusaki、Kosuke Nakashima、Miki Shimomura、Masahiro Kawada、Yasuyuki Matsushima、Shin-ichi Hirashima、Tsuyoshi Miura

  DOI：10.1016/j.tetlet.2023.154375

  日期：2023.3

  An organocatalyst derived from quinine efficiently promoted an asymmetric Henry reaction between α,β -unsaturated trifluoromethyl ketones and nitromethane, resulting in corresponding and highly functionalized products with excellent yields and high enantioselectivities (up to 94% ee).

  一种源自奎宁的有机催化剂有效地促进了 α,β-不饱和三氟甲基酮和硝基甲烷之间的不对称亨利反应，从而产生了相应的高度功能化的产物，具有优异的收率和高对映选择性（高达 94% ee）。
• Controllable Skeletal and Peripheral Editing of Pyrroles with Vinylcarbenes
  作者：Yong Yang、Qingmin Song、Paramasivam Sivaguru、Zhaohong Liu、Dan Shi、Tian Tian、Graham de Ruiter、Xihe Bi

  DOI：10.1002/anie.202401359

  日期：——

  The skeletal editing of azaarenes through insertion, deletion, or swapping of single atoms has recently gained considerable momentum in chemical synthesis. Here, we describe a practical skeletal editing strategy using vinylcarbenes in‐situ generated from trifluoromethyl vinyl N‐triftosylhydrazones, leading to the first dearomative skeletal editing of pyrroles through carbon‐atom insertion. Furthermore, depending on the used catalyst and substrate, three types of peripheral editing reactions of pyrroles are also disclosed: α‐ or γ‐selective C–H insertion, and [3+2] cycloaddition. These controllable molecular editing reactions provide a powerful platform for accessing medicinally relevant CF3‐containing N‐heterocyclic frameworks, such as 2,5‐dihydropyridines, piperidines, azabicyclo[3.3.0]octadienes, and allylated pyrroles from readily available pyrroles. Mechanistic insights from experiments and density functional theory (DFT) calculations shed light on the origin of substrate‐ or catalyst‐controlled chemo‐ and regioselectivity as well as the reaction mechanism.
• Isothiourea-mediated asymmetric Michael-lactonisation of trifluoromethylenones: a synthetic and mechanistic study
  作者：Louis C. Morrill、James Douglas、Tomas Lebl、Alexandra M. Z. Slawin、David J. Fox、Andrew D. Smith

  DOI：10.1039/c3sc51791h

  日期：——

  HBTM-2.1 promotes the catalytic asymmetric intermolecular Michael-lactonisation of arylacetic acids and trifluoromethylenones in the presence of pivaloyl chloride, giving C(6)-trifluoromethyldihydropyranones with high diastereo- and enantiocontrol (up to 95 : 5 dr and >99% ee) that are readily derivatised to diverse synthetic building blocks containing trifluoromethyl-stereogenicity. Kinetic studies indicate the reaction is first order with respect to both in situ formed mixed anhydride and catalyst concentration, with a primary kinetic isotope effect observed using α,α-di-deuterio 4-fluorophenylacetic acid, consistent with rate determining deprotonation of an intermediate acyl isothiouronium ion.

  HBTM-2.1在有庚酰氯存在的情况下，促进了芳基乙酸和三氟甲烯酮的催化不对称分子间迈克尔-内酯化反应，生成高二者立体选择性和对映选择性的C(6)-三氟甲基二氢吡喃酮（达到95 : 5的dr和>99% ee），这些产物可以方便地转化为含有三氟甲基手性基团的多样合成构件。动力学研究表明，反应对原位生成的混合酸酐和催化剂浓度均为一级反应，同时在使用α,α-二氘基4-氟苯乙酸的实验中观察到了主要的动力学同位素效应，这与中间体酰基异硫尿阳离子的去质子化作为速率限制步骤一致。