105304-62-9

Upstream product

• 2216-94-6 phenylpropynoic acid ethyl ester 
• 591-50-4 iodobenzene 
• 105836-29-1 ethyl 3-bromo-3,3-difluoropropanoate 
• 623-47-2 propynoic acid ethyl ester 
• 131981-91-4 ethyl (Z)-3-fluoropropenoate 
• 1068142-02-8 fluoro(trimethylsilyl)ketene ethyl trimethylsilyl acetal 
• 100-52-7 benzaldehyde 
• 1645-58-5 Diethyl 3-bromo-3,3-difluoropropanal diethyl acetal 

Downstream Products

• 29900-78-5 MAZ₁₇₀₂ 
• 70260-27-4 ethyl (E)-3-phenyl-3-fluoro-2-propenoate 
• 70199-99-4 ethyl 3-fluoro-3-phenylpropanoate 

Relevant academic research and scientific papers

Effect of Fluorination on Skin Sensitization Potential and Fragrant Properties of Cinnamyl Compounds

A series of three α- and three β-fluorinated representatives of the family of cinnamate-derived odorants (cinnamaldehyde (1), cinnamyl alcohol (2), and ethyl cinnamate (3)) as used as fragrance ingredients is described. Olfactive evaluation shows that the

Gold-Catalyzed Hydrofluorination of Electron-Deficient Alkynes: Stereoselective Synthesis of β-Fluoro Michael Acceptors

The gold(I)-catalyzed, stereoselective hydrofluorination of electron-deficient alkynes with triethylamine trihydrogen fluoride (Et3N·3HF) is described. Fluorinated α,β-unsaturated aldehydes, amides, esters, ketones, and nitriles were isolated i

N-heterocyclic carbene-catalysed Peterson olefination reaction

N-heterocyclic carbenes (NHCs) have been utilised as highly efficient organocatalysts to catalyse Peterson olefination reaction of aldehydes with trimethylsilylketene ethyl trimethylsilyl acetal or fluoro(trimethylsilyl)ketene ethyl trimethylsilyl acetal to produce the corresponding functionalized olefines in 34-93% yields with excellent stereoselectivities.

Hydrofluorination of alkynes catalysed by gold bifluorides

We report the synthesis of nine new N-heterocyclic carbene gold bifluoride complexes starting from the corresponding N-heterocyclic carbene gold hydroxides. A new methodology to access N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) fluoride starting from N,N′-bis(2,6-diisopropylphenyl)imidazol-2-ylidene gold(I) hydroxide and readily available potassium bifluoride is also reported. These gold bifluorides were shown to be efficient catalysts in the hydrofluorination of symmetrical and unsymmetrical alkynes, thus affording fluorinated stilbene analogues and fluorovinyl thioethers in good to excellent yields with high stereo- and regioselectivity. The method is exploited further to access a fluorinated combretastatin analogue selectively in two steps starting from commercially available reagents.

Heck reaction with ethyl (E)- and (Z)-3-fluoropropenoate

The use of monofluoro alkene substrates in the Heck reaction is relatively unknown. The reaction between ethyl E-3-fluoropropenoate or ethyl Z-3-fluoropropenoate with iodobenzene and palladium acetate produces only ethyl 3-fluoropropenoate (Z-6). Some los

Palladium(0)/copper(I)-cocatalyzed cross-coupling of the zinc reagent of ethyl 3-bromo-3,3-difluoropropionate with aryl (alkenyl) halides: An efficient stereoselective synthesis of β-fluoro-α,β-unsaturated esters

Ethyl 3-bromo-3, 3-difluoropropionate was prepared in an overall yield of 75% from the radical addition of dibromodifluoromethane to ethyl vinyl ether under Na2S2O4 initiation, followed by oxidation of the acetal with Caro acid. The treatment of 1 with active zinc dust in anhydrous DMF at room temperature produced the zinc reagent ZnBrCF2CH2CO2C2H5 (2). The cross coupling of the zinc reagent 2 with aryl (alkenyl) halides (R-X) in DMF using Pd(0)-Cu(I) as cocatalyst stereoselectively provided the β-fluoro-α,β- unsaturated esters (RCF=CHCO2C2H5 4) directly and in moderate yields. An E/Z ratio ranging from 3:2 to 1:0 was observed. This is the first example that Cu(I) can improve the selectivity of the cross-coupling reaction. Mechanistic studies revealed that zinc reagent 2 underwent stereoselective elimination to produce (Z)-1-fluoro-2-(ethoxycarbonyl)ethenylzinc reagent 6, and then the cross-coupling of 6 with aryl(alkenyl) halides under palladium(O) catalysis afforded the β-fluoro-α,β-unsaturated esters 4.

Enantioselective synthesis of β-fluoro-β-aryl-α-aminopentenamides by organocatalytic [2,3]-sigmatropic rearrangement

The tetramisole-promoted catalytic enantioselective [2,3]-sigmatropic rearrangement of quaternary ammonium salts bearing a (Z)-3-fluoro-3-arylprop-2-ene group generates, after addition of benzylamine, a range of β-fluoro-β-aryl-α-aminopentenamides containing a stereogenic tertiary fluorine substituent. Cyclic and acyclic nitrogen substituents as well as various aromatic substituents are tolerated, giving the β-fluoro-β-aryl-α-aminopentenamide products in up to 76% yield, 96:4 dr, and 98:2 er.

Mono-hydrofluorination of Electrophilic Alkynes by the Liquid Bishasic CsF-H2O-DMF System (DMF = N,N-dimethylformamide)

CsF induces the addition of HF in fair yields to activated acetylenic triple bonds in a DMF-water bishasic medium (DMF = N,N-dimethylformamide); in a homogeneous DMF-water mixture, no addition is observed.

Gold N-Heterocyclic Carbene Catalysts for the Hydrofluorination of Alkynes Using Hydrofluoric Acid: Reaction Scope, Mechanistic Studies and the Tracking of Elusive Intermediates

An efficient and chemoselective methodology deploying gold-N-heterocyclic carbene (NHC) complexes as catalysts in the hydrofluorination of terminal alkynes using aqueous HF has been developed. Mechanistic studies shed light on an in situ generated catalyst, formed by the reaction of Br?nsted basic gold pre-catalysts with HF in water, which exhibits the highest reactivity and chemoselectivity. The catalytic system has a wide alkyl substituted-substrate scope, and stoichiometric as well as catalytic reactions with tailor-designed gold pre-catalysts enable the identification of various gold species involved along the catalytic cycle. Computational studies aid in understanding the chemoselectivity observed through examination of key mechanistic steps for phosphine- and NHC-coordinated gold species bearing the triflate counterion and the elusive key complex bearing a bifluoride counterion.

Gold-Catalyzed Hydrofluorination of Internal Alkynes Using Aqueous HF

The gold-catalyzed hydrofluorination reaction of internal alkynes using hydrofluoric acid is reported. Notably, those conditions use one of the most economical sources of HF and are free of additional additives. Both symmetrical and unsymmetrical internal alkynes can be utilized, and the use of alkynes bearing a fluorinated group at the propargylic position as substrates allowed for a regioselective hydrofluorination reaction.