57918-94-2

Upstream product

• 98837-36-6 methyl 3-hydroxy-2-methylenebutyrate 
• 99-90-1 para-bromoacetophenone 
• 598-32-3 2-hydroxy-3-butene 
• 1927-95-3 4-bromophenyl acetate 
• 13329-40-3 4-Iodoacetophenone 
• 890522-64-2 C₈H₁₀N₂O₃S 
• 149104-90-5 4-acetylphenylboronic acid 
• 78-94-4 methyl vinyl ketone 
• 99-91-2 para-chloroacetophenone 
• 2550-26-7 4-Phenyl-2-butanone 
• 75-36-5 acetyl chloride 

Downstream Products

• 1263314-54-0 4-[4-(1-hydroxy-ethyl)-phenyl]-butan-2-one 
• 30435-49-5 4-(4-ethyl-phenyl)-butan-2-one 
• 1587619-81-5 1-(4-hexanoylphenyl)octan-3-one 

Relevant academic research and scientific papers

Pd-Catalyzed Regio- and Stereoselective sp3 C?H Arylation of Primary Aliphatic Amines: Mechanistic Studies and Synthetic Applications

The Pd-catalyzed γ-position sp3?C?H arylation of primary amines bearing an aliphatic chain or cycloalkyl substituent and related mechanistic studies are disclosed. 3-Bromo-2-hydroxybenzaldehyde plays a key role in γ-position sp3?C?H arylation as a transient directing group (TDG) to assist the regio- and stereoselective C?H activation of a Pd catalyst, and the development of a tandem reaction to transform 1°-amines into γ-aryl-substituted ketones demonstrates synthetic utility. Density functional theory (DFT)-based calculations revealed the detailed reaction mechanism and the origins of the high selectivity (γ-position and cis-only). The X-ray crystal structure of the isolated endo-palladacycle intermediate supported the DFT results, and a kinetic isotope experiment confirmed the results of DFT calculations indicating that the C?H activation step via simultaneous palladation and deprotonation is rate-determining.

Controlling olefin isomerization in the heck reaction with neopentyl phosphine ligands

The use of neopentyl phosphine ligands was examined in the coupling of aryl bromides with alkenes. Di-tert-butylneopentylphosphine (DTBNpP) was found to promote Heck couplings with aryl bromides at ambient temperature. In the Heck coupling of cyclic alkenes, the degree of alkene isomerization was found to be controlled by the choice of ligand with DTBNpP promoting isomerization to a much greater extent than trineopentylphosphine (TNpP). Under optimal conditions, DTBNpP provides high selectivity for 2-aryl-2,3-dihydrofuran in the arylation of 2,3-dihydrofuran, whereas TNpP provided high selectivity for the isomeric 2-aryl-2,5-dihydrofuran. A similar complementary product selectivity is seen in the Heck coupling of cyclopentene. Heck coupling of 2-bromophenols or 2-bromoanilides with 2,3-dihydrofurans affords 2,5-epoxybenzoxepin and 2,5-epoxybenzazepins, respectively.

Aerobic oxidative coupling between carbon nucleophiles and allylic alcohols: A strategy to construct β-(hetero)aryl ketones and aldehydes through hydrogen migration

Wacker heck of a reaction: A highly efficient PdII-catalyzed intermolecular oxidative-coupling reaction is reported, inspired by the fundamental Heck and Wacker processes. The (hetero)aryl-PdX species, originating from C-H activation step or desulfonyl hydrazides, coupled with allylic alcohols by using oxygen as the sole oxidant (see scheme). Copyright

Synthesis of β-aryl ketones by heck arylation of allylic alcohols catalysed by a MCM-41-supported bidentate nitrogen palladium complex

The Heck arylation reaction of aryl iodides with allylic alcohols catalysed by an mesoporous silica (MCM-41)-supported bidentate nitrogen palladium complex [MCM-41-2N-Pd(OAc)2] proceeded smoothly in the presence of tetrabutylammonium chloride (TBAC) in DMF to afford β-aryl ketones in good to excellent yields. This heterogeneous palladium catalyst can be recovered by simple filtration and reused several times without any decrease in activity.

C-O hydrogenolysis catalyzed by Pd-PMHS nanoparticles in the company of chloroarenes

Catalytic Pd(OAc)2 and polymethylhydrosiloxane (PMHS), in conjunction with aqueous KF, and a catalytic amount of an aromatic chloride, effects the chemo-, regio-, and stereoselective deoxygenation of benzylic oxygenated substrates at room temperature in THF. Preliminary mechanistic experiments suggest the process to involve palladium-nanoparticle-catalyzed hydrosilylation followed by C-O reduction. The chloroarene additive appears to facilitate the hydrogenolysis process through the slow controlled release of HCl.

Direct cobalt-catalyzed conjugate addition of functionalized aryl halides and triflates: A new strategy for the conjugate addition onto methyl vinyl ketone

An efficient cobalt-catalyzed method for the direct conjugate addition of functionalized aryl halides or triflates onto methyl vinyl ketone is described. The experimentally simple procedure relies on the use of a catalytic system consisting of CoBr2(Bpy) and zinc and does not require the preformation of a stoichiometric organometallic species. The approach described herein displays considerable functional-group compatibility at good to excellent yields. Georg Thieme Verlag Stuttgart.

Heck-type coupling vs. conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyl compounds: A systematic investigation

The competition between Heck-type coupling and conjugate addition in phosphine-rhodium catalyzed reactions of aryl boronic acids with α,β-unsaturated carbonyls has been systematically investigated in a toluene-H2O biphasic system. Aside from the intrinsic nature of rhodium and the enolization of carbonyls, the phosphine supporting ligand on rhodium, the ratio of aryl boronic acid to α,β-unsaturated carbonyl and the pH value of the aqueous phase were found to affect the competition significantly. Highly selective rhodium-based catalyst systems have therefore been developed for both Heck-type coupling and conjugate addition by synergistically tuning the supporting ligand, the boronic acid to olefin ratio and other reaction conditions. Conjugate addition with selectivity >99% and Heck-type coupling with selectivity of up to 100%, 98% and 84% for acrylates, acrylamides and methyl vinyl ketone, respectively, could be achieved in the rhodium-catalyzed reactions of aryl boronic acids with α,β- unsaturated carbonyls using the corresponding optimized rhodium-based catalyst systems. The Royal Society of Chemistry.

Synthesis of β-aryl ketones by tetraphosphine/palladium catalysed Heck reactions of 2- or 3-substituted allylic alcohols with aryl bromides

Through the use of [PdCl(C3H5)]2/cis,cis,cis-1,2,3,4-tetrakis(diphenylphosphinomethyl)cyclopentane as a catalyst, a range of aryl bromides undergoes Heck reaction using 2- or 3-subtituted allylic alcohols. With these sterically congested alkenes, the selective formation of β-aryl ketones was observed when appropriate reaction conditions were used. The influence of the functional group on the aryl bromide and of the base on the selectivity is remarkable. With several substrates, much higher selectivities were obtained using NaHCO3 instead of K2CO3 as base. Furthermore, this catalyst can be used at low loading with several substrates.

Homeopathic ligand-free palladium as a catalyst in the heck reaction. A comparison with a palladacycle

(Matrix presented) Ligand-free Pd(OAc)2 can be used as a catalyst in the Heck reaction of aryl bromides as long as the amount of catalyst is kept between 0.01 and 0.1 mol %. At higher concentrations palladium black forms and the reaction stops. The actual catalyst is monomeric. Palladacycles merely serve as a source of ligand-free palladium in Heck reactions of aryl bromides.

Nickel-catalyzed electrochemical arylation of activated olefins

Nickel-catalyzed electrochemical conjugate additions of substituted aryl bromides to activated olefins under recently optimized reaction conditions are reported. Good to high yields were obtained, whatever the nature of substituents in the meta- and para-positions of the benzene ring. In the ortho-substituted series, yields were good with electron-donating substituents, but low with electron-withdrawing groups. The activation of aryl chlorides and the sequential functionalization of aryl dihalides were also investigated.