80967-16-4Relevant articles and documents
Visible-light promoted atom transfer radical addition?elimination (ATRE) reaction for the synthesis of fluoroalkylated alkenes using DMA as electron-donor
Xu, Wen-Wen,Wang, Le,Mao, Ting,Gu, Jiwei,Li, Xiao-Fei,He, Chun-Yang
supporting information, (2020/02/11)
Here, we describe a mild, catalyst-free and operationally-simple strategy for the direct fluoroalkylation of olefins driven by the photochemical activity of an electron donor?acceptor (EDA) complex between DMA and fluoroalkyl iodides. The significant advantages of this photochemical transformation are high efficiency, excellent functional group tolerance, and synthetic simplicity, thus providing a facile route for further application in pharmaceuticals and life sciences.
Fluoroalkenylation of boronic acids: Via an oxidative Heck reaction
Lee, Da Seul,Cho, Eun Jin
, p. 4317 - 4325 (2019/05/06)
A fluoroalkenylation of boronic acids with fluoroalkyl alkenes has been developed. The Pd-catalyzed oxidative Heck coupling reaction proceeds under an oxygen atmosphere at room temperature, in the absence of a base and/or a ligand, showing excellent practicality of the process. This simple transformation is highly stereoselective to provide only E-isomers. In addition to the general approach using alkenes with functionalized fluoroalkyl reagents, this method, by transferring an aromatic system to the electron-deficient fluoroalkyl alkene, provides an efficient alternative method to yield valuable organofluorines.
Organic Dye-Catalyzed Atom Transfer Radical Addition-Elimination (ATRE) Reaction for the Synthesis of Perfluoroalkylated Alkenes
Tiwari, Deo Prakash,Dabral, Saumya,Wen, Jian,Wiesenthal, Jan,Terhorst, Steven,Bolm, Carsten
supporting information, p. 4295 - 4298 (2017/08/23)
An atom transfer radical addition elimination (ATRE) reaction of terminal alkenes with perfluoroalkyl halides under visible light is described. The photoredox catalysis with Eosin Y provides perfluoroalkenes in good yields. The reaction has been utilized
Copper-Catalyzed Decarboxylative Difluoroalkylation and Perfluoroalkylation of α,β-Unsaturated Carboxylic Acids
Lai, Yin-Long,Lin, Dian-Zhao,Huang, Jing-Mei
, p. 597 - 605 (2017/04/26)
Copper-catalyzed decarboxylative difluoroalkylation and perfluoroalkylation of α,β-unsaturated carboxylic acids is described. Promoted by dialkyl phosphite, this novel reaction affords fluoroalkylated motifs with excellent stereoselectivity and broad substrate scope under mild reaction conditions from readily available fluoroalkyl iodides and bromides. Preliminary mechanism study suggests that radical pathway was involved in the catalytic cycle and dialkyl phosphite had played an indispensable role in this reaction.
An efficient synthesis of perfluoroalkenylated aryl compounds via Pincer-Pd catalyzed Heck couplings
Feng, Jie,Cai, Chun
, p. 6 - 10 (2013/03/28)
Heck couplings of aryl halides with fluoroalkyl-substituted ethylenes catalyzed by Pincer Palladium complex were described. A variety of fluorous ponytail-substituted aromatics were obtained with moderate to excellent yields. Moreover, the catalyst can be easily separated from the reaction mixture by F-SPE technique and reused three times without significant loss of activity.
Siloxane based syntheses of fluorous ethenes and their tandem Heck reactions with aryl iodides
Csapo, Agnes,Rabai, Jozsef
, p. 79 - 85,7 (2020/09/16)
Perfluoroalkyl-ethenes (RfnCHCH2, 6a-c; a, n = 4; b, n = 6; c, n = 8) were prepared in good isolated yields (67-89%) and high purity (GC assay > 98%) from various fluorinated organosilanes in fluoride-anion assisted protodesilylation reactions. The environmentally more benign 'KF/NEt3/H2O' reagent combination introduced here was found as an effective substitute for the commonly used tetrabutylammonium- fluoride trihydrate (TBAF·3H2O) as a fluoride source. Fluorous styrenes ((E)-RfnCHCHAr, 8) were then prepared in good isolated yields (58-93%/iodoarene) and purities (GC assay > 95%) with the Pd(0) catalyzed Heck coupling of iodoarenes (Ar-I, 7) and perfluoroalkyl-ethenes generated in situ by the fluoride assisted cleavage of (β-perfluoroalkyl- α-iodo-ethyl)-siloxane ([RfnCH2CH(I)SiMe 2]2O, 3) precursors in DMF solution at elevated temperatures. They are accessible by the one-pot reaction of dimethylvinylchlorosilane (CH2CHSiMe2Cl, 2) and perfluoroalkyl iodides (Rfn-I, 1) as we reported earlier. Similarly, the radical chain addition of C8F17I to CH 2CHSi(OMe)3 (9) gave (β-perfluorooctyl-α-iodo- ethyl)-trimethoxysilane ([C8F17CH2CH(I)]Si(OMe) 3, 10) in good yield, which then was reacted with silica gel in dry toluene to obtain an SiO2-bonded (perfluorooctyl)ethene surrogate [silica(O)3SiCH(I)CH2C8F17, 11]. The fluoride assisted cleavage of 11 and tandem Heck reaction with iodobenzene afforded the appropriate cross-coupled product (E)-C8F 17CHCHPh.
Hiyama coupling reaction of fluorous alkenyl-fluorosilanes: Scope and mechanistic considerations
Rábai, József,Csapó, ágnes,Bodor, Andrea
, p. 85 - 92 (2012/05/20)
Novel fluorous alkenyl-fluorosilanes (CnF 2n+1CHCHSiMe2F; n = 4, 6, 8; 5a-c) were synthetized in a three step procedure from perfluoroalkyliodides and dimethylvinylchlorosilane. They were first reacted with iodobenzene at room temperature in Hiyama coupling reaction (DMF, Pd(OAc)2, TBAF, 72 h) to afford the appropriate ω-perfluoroalkyl-styrenes (CnF2n+1CHCHC 6H5, n = 4, 6, 8); then the reactivity of 5a with monosubstituted iodobenzenes was studied. The coupling reaction of 5a with o-substituted iodobenzenes usually failed, while that of with the m- and p-substituted ones gave fluorous styrenes [m- or p-(C4F 9CHCH)C6H4X], independently of the electronic effect of their substituent (X = Br, CF3, CH3, OCH 3). These volatile products can easily be isolated by steam-distilltaion and purified further by distillation. The mechanism of the above coupling reactions was a pure Hiyama type involving fluoride-ion induced transmetallation without any Heck type contribution, since no coupling product of C6F13CHCH2 and C6H5I was observed in blank control experiments using similar conditions (DMF, TBAF, Pd(OAc)2, 72 h, 25°C).
Radical allylation, vinylation, alkynylation, and phenylation reactions of α-halo carbonyl compounds with organoboron, organogallium, and organoindium reagents
Takami, Kazuaki,Usugi, Shin-Ichi,Yorimitsu, Hideki,Oshima, Koichiro
, p. 824 - 839 (2007/10/03)
Allylic gallium and indium reagents are found to mediate radical allylation reactions of α-iodo or α-bromo carbonyl compounds. Treatment of benzyl bromoacetate with allylgallium, prepared from allylmagnesium chloride and gallium trichloride, in the presence of triethylborane provided benzyl 4-pentenoate in excellent yield. Addition of water as a co-solvent improved the yields of allylated products. Allylic indium reagents are also useful and can replace the gallium reagents. A diallylborane reagent can allylate an α-iodo ester in good yield. Alkenylation reactions of α-halo carbonyl compounds with alkenylindium proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties and styryl groups were introduced by this method. The carbon-carbon double bond geometry of the alkenylindiums was retained during the alkenylation. Preparation of an alkenylindium via a hydroindation of 1-alkyne and subsequent radical alkenylation established an efficient one-pot strategy. Radical alkynylations and phenylations with organoindium reagents are disclosed herein.
Radical alkenylation of α-halo carbonyl compounds with alkenylindiums
Takami, Kazuaki,Yorimitsu, Hideki,Oshima, Koichiro
, p. 4555 - 4558 (2007/10/03)
(Chemical equation presented) Alkenylation reaction of α-halo carbonyl compounds with alkenylindiums proceeded via a radical process in the presence of triethylborane. Unactivated alkene moieties as well as a styryl group could be introduced by this metho
