2-methyl-2-(trifluoromethyl)-2,3-dihydro-1H-inden-1-one

• 分子结构分类: 有机化合物 - 苯类化合物 - 茚满类
• 英文名称: 2-methyl-2-(trifluoromethyl)-2,3-dihydro-1H-inden-1-one
• 英文别名: 2-methyl-2-(trifluoromethyl)-1-indanone；2-methyl-2-(trifluoromethyl)-3H-inden-1-one
• 化学式: C₁₁H₉F₃O
• 分子量: 214.187
• InChiKey: VUGYHLBEMLXCBF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.2
• 重原子数：
  15
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.36
• 拓扑面积：
  17.1
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  1-茚酮 在 三乙基硼 、 2-苯基-1,3,2-苯并二氧杂戊硼烷 、 potassium hydride 作用下， 反应 4.5h， 生成 2-methyl-2-(trifluoromethyl)-2,3-dihydro-1H-inden-1-one
  参考文献：
  名称：

  New Method for Trifluoromethylation of Enolate Anions and Applications to Regio-, Diastereo- and Enantioselective Trifluoromethylation

  摘要：

  Assessment was made of the effectiveness of different boron Lewis acids in mediating the trifluoromethylation of reactive enolate anions with S- and Se-(trifluoromethyl)chalcogen salts. Treatment of potassium or lithium enolates derived in situ from carbonyl compounds or enol trimethylsilyl ethers with S-(trifluoromethyl)dibenzothiophenium triflate (1) in the presence of 2-phenyl-1,3,2-benzodioxaborole (4) produced trifluoromethylated carbonyl compounds in high yields. Iq this manner, various alpha-CF3 ketones, gamma-CF3-alpha,beta-unsaturated ketones, and an alpha-CF3 ester were synthesized. Perfluorooctylation was similarly conducted using S-(perfluorooctyl)dibenzothiophenium triflate and 4. Thus, a balance of the reactivity of the reactants was essential for these electrophilic perfluoroalkylations. The deprotonation of 2-methylcyclohexanone with KN(SiMe(3))(2) followed by trifluoromethylation gave the 6-trifluoromethylated product regioselectively. In the trifluoromethylation of potassium enolate 16 of 4,4a,5,6,7,8-hexahydro-4a-methyl-2(3H)-naphthalenone, the use of bulky 2-mesitylphenanthro[9,10-d]-1,3,2-dioxaborole (15) led to the diastereo-selective formation of the thermodynamically less stable CF3-isomer 17 beta. For enantioselective trifluoromethylation, optically active (S)-4-phenyldinaphtho[2,1-d:1',2'-f][1,3,2]dioxaborepin(19) and its 3,3'-diphenyl derivative 20 were synthesized. The trifluoromethylation of the potassium enolate of propiophenone with 1 in the presence of 20 afforded optically active alpha-CF3-propiophenone in 45% ee yield. Thus, a new and versatile method for selective trifluoromethylation has been developed.

  DOI：

  10.1021/jo00098a030

文献信息

• Combining Photoredox‐Catalyzed Trifluoromethylation and Oxidation with DMSO: Facile Synthesis of α‐Trifluoromethylated Ketones from Aromatic Alkenes
  作者：Ren Tomita、Yusuke Yasu、Takashi Koike、Munetaka Akita

  DOI：10.1002/anie.201403590

  日期：2014.7.7

  organic compounds with a trifluoromethyl group. A new and facile synthesis of ketones with a trifluoromethyl substituent in the α‐position proceeds through a one‐pot photoredox‐catalyzed trifluoromethylation–oxidation sequence of aromatic alkenes. Dimethyl sulfoxide (DMSO) serves as a key and mild oxidant under these photocatalytic conditions. Furthermore, an iridium photocatalyst, fac[Ir(ppy)3] (ppy=2‐phenylpyridine)

  三氟甲基化的酮是具有三氟甲基的有机化合物的有用的结构单元。通过一锅光氧化还原催化的芳香族烯烃的三氟甲基化-氧化顺序，可以进行新的且简便的α位三氟甲基取代基酮的合成。在这些光催化条件下，二甲基亚砜（DMSO）用作关键和温和的氧化剂。此外，事实证明，铱光催化剂fac [Ir（ppy）3 ]（ppy = 2-苯基吡啶）对于当前的光氧化还原工艺至关重要。
• Photoredox Catalysis: A Mild, Operationally Simple Approach to the Synthesis of α-Trifluoromethyl Carbonyl Compounds
  作者：Phong V. Pham、David A. Nagib、David W. C. MacMillan

  DOI：10.1002/anie.201101861

  日期：2011.6.27

  A facile and efficient method for the α‐trifluoromethylation of carbonyl compounds and enolsilanes has been accomplished through application of a photoredox catalysis strategy. A one‐flask procedure for the direct α‐trifluoromethylation and α‐perfluoroalkylation of ketone, amide, and ester substrates as well as silylketene acetals is described (see scheme).

  通过应用光氧化还原催化策略，实现了一种简便有效的羰基化合物和烯醇硅烷的 α-三氟甲基化方法。描述了酮、酰胺和酯底物以及甲硅烷基烯酮缩醛的直接 α-三氟甲基化和 α-全氟烷基化的单烧瓶程序（参见方案）。
• Power-variable electrophilic trifluoromethylating agents. S-, Se-, and Te-(trifluoromethyl)dibenzothio-, -seleno-, and -tellurophenium salt system
  作者：Teruo Umemoto、Sumi Ishihara

  DOI：10.1021/ja00059a009

  日期：1993.3

  Te-trifluoromethylated dibenzoheterocyclic onium salts, their derivatives, and related salts were synthesized by the direct fluorination of a mixture of 2-[(trifluoromethyl)thio- or seleno]biphenyls and triflic acid (TfOH) or HBF 4 etherate, by treatment of the corresponding sulfoxides and selenoxides with Tf 2 O by a new type of tellurium activation of 2-[(trifluoromethyl)telluro]biphenyls with Tf 2 O and (CH

  S-、Se-和 Te-三氟甲基化二苯并杂环鎓盐、它们的衍生物和相关盐是通过 2-[（三氟甲基）硫代或硒代]联苯和三氟甲磺酸 (TfOH) 或 HBF 的混合物的直接氟化合成的4 醚化物，通过使用 Tf 2 O 和 (CH 3 ) 2 SO 对 2-[(三氟甲基) 碲] 联苯进行新型碲活化，或通过鎓的衍生，用 Tf 2 O 处理相应的亚砜和硒氧化物得到的盐。反应性检查表明，与非杂环盐相比，三氟甲基杂环盐具有很强的反应性，并表明该杂环盐体系可作为广泛适用的三氟甲基化剂的来源
• Synthesis of α-Trifluoromethyl Ketones via the Cu-Catalyzed Trifluoromethylation of Silyl Enol Ethers Using an Electrophilic Trifluoromethylating Agent
  作者：Lun Li、Qing-Yun Chen、Yong Guo

  DOI：10.1021/jo500713f

  日期：2014.6.6

  A method has been developed for the synthesis of α-trifluoromethyl ketones via the Cu-catalyzed trifluoromethylation of silyl enol ethers with an electrophilic trifluoromethylating agent, which produces a trifluoromethyl radical.

  已经开发了一种方法，该方法通过使用亲电子的三氟甲基化剂经Cu催化的甲硅烷基烯醇醚的三氟甲基化来合成α-三氟甲基酮，从而产生三氟甲基基团。
• Mild Electrophilic Trifluoromethylation of β-Ketoesters and Silyl Enol Ethers with 5-Trifluoro Methyldibenzothiophenium Tetrafluoroborate
  作者：Jun-An Ma、Dominique Cahard

  DOI：10.1021/jo034881e

  日期：2003.10.1

  to excellent yields. In a second approach, 5-trifluoromethyldibenzothiophenium tetrafluoroborate and tetrabutylammonium difluorotriphenylstannate were used for efficient electrophilic trifluoromethylation of various silyl enol ethers leading to the corresponding alpha-trifluoromethyl ketones in good to high yields.

  在相转移催化剂的存在下，用5-三氟甲基二苯并噻吩四氟硼酸酯有效地将环状和无环β-酮酸酯三氟甲基化，从而以良好或优异的收率得到相应的α-取代的α-取代的α-三氟甲基β-酮酸酯。在第二种方法中，将四氟硼酸5-三氟甲基二苯并噻吩鎓盐和二氟三苯基锡四丁基铵用于各种甲硅烷基烯醇醚的有效亲电子三氟甲基化，从而以良好或高收率得到相应的α-三氟甲基酮。