55009-92-2

Upstream product

• 355-43-1 n-perfluorohexyl iodide 
• 103-64-0 bromostyrene 
• 100-42-5 styrene 
• 55591-23-6 1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane-1-sulfonyl chloride 
• 536-74-3 phenylacetylene 
• 355-41-9 perfluoro-n-hexyl chloride 
• 591-50-4 iodobenzene 
• 25291-17-2 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooct-1-ene 
• 108-86-1 bromobenzene 
• 98-80-6 phenylboronic acid 
• 335-56-8 1-bromo-1,1,2,2,3,3,4,4,5,5,6,6,6-tridecafluorohexane 
• 140-10-3 (E)-3-phenylacrylic acid 
• 101349-79-5 2-phenylvinyl iodide 
• 42599-24-6 E-styryl iodide 

Relevant academic research and scientific papers

Fluoroalkenylation of boronic acids: Via an oxidative Heck reaction

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.

Copper-Catalyzed Decarboxylative Difluoroalkylation and Perfluoroalkylation of α,β-Unsaturated Carboxylic Acids

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.

Practical Photocatalytic Trifluoromethylation and Hydrotrifluoromethylation of Styrenes in Batch and Flow

Styrenes represent a challenging class of substrates for current radical trifluoromethylation and hydrotrifluoromethylation methods due to a myriad of potential side reactions. Herein, we describe the development of mild, selective and broadly applicable photocatalytic trifluoromethylation and hydrotrifluoromethylation protocols for these challenging substrates. The methods use fac-Ir(ppy)3, visible light and inexpensive CF3I and can be applied to a diverse set of vinylarene substrates. The use of continuous-flow photochemical reaction conditions allowed to reduce the reaction time and increase the reaction selectivity.

METHOD FOR PRODUCING FLUORINE-CONTAINING OLEFIN

PROBLEM TO BE SOLVED: To provide a method for simply and efficiently producing a fluorine-containing olefin having a perfluoro-alkyl group under a mild condition. SOLUTION: Provided is a method for producing a compound represented by the following formula (51) by reacting a compound represented by the following formula (21) and a compound represented by the following formula (31) under the presence of a metal-carbene complex compound (10) having an olefin metathesis reaction activity. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT

A general synthesis of fluoroalkylated alkenes by palladium-catalyzed Heck-type reaction of fluoroalkyl bromides

An efficient palladium-catalyzed Heck-type reaction of fluoroalkyl halides, including perfluoroalkyl bromides, trifluoromethyl iodides, and difluoroalkyl bromides, has been developed. The reaction proceeds under mild reaction conditions with high efficiency and broad substrate scope, and provides a general and straightforward access to fluoroalkylated alkenes which are of interest in life and material sciences.

Stable but reactive perfluoroalkylzinc reagents: Application in ligand-free copper-catalyzed perfluoroalkylation of aryl iodides

The aromatic perfluoroalkylation catalyzed by a copper(I) salt with bis(perfluoroalkyl)zinc reagents Zn(RF)2(DMPU)2, which were prepared and then isolated as a stable white powder from perfluoroalkyl iodide and diethylzinc, was accomplished to provide the perfluoroalkylated products in good-to-excellent yields. The advantages of this reliable and practical catalytic reaction are 1) airstable and easy-to-handle bis(perfluoroalkyl)zinc reagents can be utilized, 2) the reagent is reactive and hence the operation without activators and ligands is simple, and 3) not only trifluoromethylation but also perfluoroalkylation can be attained.

An efficient synthesis of perfluoroalkenylated aryl compounds via Pincer-Pd catalyzed Heck couplings

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

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

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).

Nickel(0)-catalyzed fluoroalkylation of alkenes, alkynes, and aromatics with perfluoroalkyl chlorides

Treatment of perfluoroalkyl chlorides (RFCl) with alkenes, alkynes, or aromatics in the presence of 0.1 equiv of nickel dichloride, 1.5 equiv of zinc powder, and 0.4 equiv of triphenylphosphine in DMF at 95-100 °C for 6-8 h give the correspondi