30724-22-2Relevant articles and documents
Facile diversification of simple benzo[b]thiophenes via thienobenzyne intermediates
Morita, Takamoto,Yoshida, Suguru,Kondo, Masakazu,Matsushita, Takeshi,Hosoya, Takamitsu
, p. 81 - 84 (2017)
Thienobenzynes, which are thiophene-fused novel benzyne species, are efficiently generated via an iodine-magnesium exchange reaction of ortho-iodoaryl triflate-type precursors using a silylmethyl Grignard reagent as the activator. The method allows for facile preparation of a diverse range of multisubstituted benzothiophenes from readily available simple benzothiophenes.
Oxidation of fluoroalkyl alcohols using sodium hypochlorite pentahydrate [1]
Kirihara, Masayuki,Suzuki, Katsuya,Nakakura, Kana,Saito, Katsuya,Nakamura, Riho,Tujimoto, Kazuki,Sakamoto, Yugo,Kikkawa, You,Shimazu, Hideo,Kimura, Yoshikazu
, (2021/02/05)
Fluoroalkyl alcohols are effectivity oxidized to the corresponding fluoroalkyl carbonyl compounds by reaction with sodium hypochlorite pentahydrate in acetonitrile in the presence of acid and nitroxyl radical catalysts. Although the reaction proceeded slower under a nitroxyl radical catalyst- free condition, the desired carbonyl compounds were obtained in high yields. For the reaction with fluoroalkyl allylic alcohols, the corresponding α,β-epoxyketone hydrates were obtained in high yields.
Highly enantioselective construction of CF3-bearing all-carbon quaternary stereocenters: Hiral spiro-fused bisoxazoline ligands with 1,1′-binaphthyl sidearm for asymmetric Michael-type Friedel-Crafts reaction
Bao, Robert Li-Yuan,Fu, Kang,Shi, Lei
supporting information, (2021/11/27)
A novel class of chiral spiro-fused bisoxazoline ligands possessing a deep chiral pocket was prepared. The developed ligands have been employed in the nickel-catalyzed highly enantioselective Michael-type Friedel-Crafts reaction, affording the products bearing a trifluoromethylated all-carbon quaternary stereocenter with moderate to excellent yields (up to 99%) and good to excellent enantioselectivies (up to > 99.9% ee). Moreover, a proposed model of chiral pocket revealed that the attack of indole from the Re-face of β-CF3-β-disubstituted nitroalkene was favorable.
Palladium-catalyzed fluoroacylation of (Hetero)arylboronic acid with fluorothioacetates at ambient temperature
Ban, Shu-Rong,Cao, Ya-Fang,Dai, Hui-Xiong,Wang, Xing,Xu, Hui,Yi, Xing
supporting information, (2020/03/23)
A palladium-catalyzed fluoroacylation of (hetero)aryl boronic acid with the fluorothioacetates is described at ambient temperature. A variety of aryl, and heteroaryl boronic acids are compatible in the reaction, affording the corresponding fluoroalkyl ketones in moderate to good yields. Further late-stage di-, and trifluoroacylation of drug molecule clofibrate and estrone demonstrated the synthetic practicability of this protocol.2009 Elsevier Ltd. All rights reserved.
Selective Acylation of Aryl- A nd Heteroarylmagnesium Reagents with Esters in Continuous Flow
Heinz, Benjamin,Djukanovic, Dimitrije,Ganiek, Maximilian A.,Martin, Benjamin,Schenkel, Berthold,Knochel, Paul
supporting information, p. 493 - 496 (2020/01/31)
A selective acylation of readily accessible organomagnesium reagents with commercially available esters proceeds at convenient temperatures and short residence times in continuous flow. Flow conditions allow us to prevent premature collapse of the hemiacetal intermediates despite noncryogenic conditions, thus furnishing ketones in good yields. Throughout, the coordinating ability of the ester and/or Grignard was crucial for the reaction outcome. This was leveraged by the obtention of several bisaryl ketones using 2-hydroxy ester derivatives as substrates.
CARBENE MASS TAGGING
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Page/Page column 22, (2020/12/07)
The disclosure relates to a diazirine precursor mass tag compound represented by structural formula (I). Also disclosed is a method for detecting analytes in a sample, comprising derivatizing the analytes with the compound of formula (I), and detecting th
Fluoroform: an Efficient Precursor for the Trifluoromethylation of Aromatic Esters by Sodium Diisopropylamide with Trialkylamines
Han, Zhaomeng,Chen, Sihan,Tu, Yongjun,Lian, Xiongdong,Li, Gongyong
supporting information, p. 4658 - 4661 (2019/08/07)
The trifluoromethanide anion is the postulated key intermediate in nucleophilic trifluoromethylation reactions. It is believed to be incompatible with Na+ cation due to the strong Na–F bond. However, herein we demonstrate that it could be prepared for the first time. Trialkylamines can be used as cation chelating agents to stabilize the isolated –CF3 ion to realize trifluoromethylation reaction. With this strategy, trifluoromethyl aromatic ketones could be effectively synthesized from fluoroform and aromatic esters with diisopropyl aminosodium (NaDA) and trialkylamines.
Oxidation of α-trifluoromethyl and non-fluorinated alcohols: Via the merger of oxoammonium cations and photoredox catalysis
Pistritto, Vincent A.,Paolillo, Joshua M.,Bisset, Kathryn A.,Leadbeater, Nicholas E.
supporting information, p. 4715 - 4719 (2018/07/06)
We present an alcohol oxidation strategy to access α-trifluoromethyl ketones (TFMKs) merging catalytic oxoammonium cation oxidation with visible-light photoredox catalysis. This work uses 4-acetamido-(2,2,6,6-tetramethyl-piperidin-1-yl)oxyl as an organic oxidant capable of generating TFMKs in good yields. The methodology serves as an improvement over previous reports of an analogous oxidation strategy requiring superstoichiometric quantities of oxidant. Both primary and secondary non-fluorinated alcohols can also be oxidised in good yields.
Enantioselective Synthesis of Trifluoromethyl α,β-Unsaturated δ-Lactones via Vinylogous Aldol-Lactonization Cascade
Crotti, Simone,Di Iorio, Nicola,Mazzanti, Andrea,Righi, Paolo,Bencivenni, Giorgio
, p. 12440 - 12448 (2018/10/09)
The novel vinylogous aldol-lactonization cascade of alkylidene oxindole with trifluoromethyl ketones is presented. The reaction, catalyzed by a bifunctional tertiary amine, provides an efficient application of the vinylogous reactivity of alkylidene oxindoles for the preparation of enantioenriched trifluoromethylated α,β-unsaturated δ-lactones.
Palladium-Catalyzed Trimethylenemethane Cycloaddition of Olefins Activated by the δ-Electron-Withdrawing Trifluoromethyl Group
Trost, Barry M.,Debien, Laurent
, p. 11606 - 11609 (2015/09/28)
α-Trifluoromethyl-styrenes, trifluoromethyl-enynes, and dienes undergo palladium-catalyzed trimethylenemethane cycloadditions under mild reaction conditions. The trifluoromethyl group serves as a unique δ-electron-withdrawing group for the activation of the olefin toward the cycloaddition. This method allows for the formation of exomethylene cyclopentanes bearing a quaternary center substituted by the trifluoromethyl group, compounds of interest for the pharmaceutical, agrochemical, and materials industries. In the diene series, the cycloaddition operates in a [3 + 4] and/or [3 + 2] manner to give rise to seven- and/or five-membered rings. This transformation greatly improves the scope of the TMM cycloaddition technology and provides invaluable insights into the reaction mechanism.
