Copper-Catalyzed C-C(O)C Bond Cleavage of Monoalkylated β-Diketone: Synthesis of α,β-Unsaturated Ketones

A new and simple route for the synthesis of α,β-unsaturated ketones via cleavage of the C-C(O)C single bond of monoalkylated β-diketone has been described. The reaction was catalyzed by copper, a cheap transition metal in a weakly basic medium (K3PO4) at room temperature. To carry out this study, we first had to synthesize the monoalkylated β-diketones 1. Afterwards, α,β-unsaturated ketones 2 were obtained with high yields around 80%. Finally, all the products were characterized by 1H NMR, 13C NMR, and HRMS spectra. .

Chemoselective Catalytic Hydrogenation of α,β-Unsaturated Ketones and α,β-Unsaturated Carboxylic Esters

The effect of catalysts P-2 00-Ni(Nickel boride) and P-2 00-Ni-M(M: Co, Fe, Cu, Sn), prepared by adopting a modified recipe, on the chemoselective hydrogenation of carbon carbon double bonds in α,β- unsaturated ketones, and the activity of catalysts P-1.80-Ni, P-2 00-Ni or P-1.80(2 00) -Ni-M(M: Pd, Co, Cu) in the selective hydrogenation of carbon carbon double bonds in α,β-unsaturated carboxylic esters, were investigated systematically. According to the experimental results, the selectivities of these catalysts toward the hydrogenation of the carbon carbon double bonds of α,β-unsaturated keones or α,β-unsaturated carboxylic esters are 96%—100% or 100%, respectively.

Doebner condensation in ionic liquids [Bmim]BF_4 and [Bpy]BF_4 to synthesize α,β-unsaturated carboxylic acid

Ionic liquids [Bmim]BF4 and [Bpy]BF4 were employed as environmentally benign media in Doebner condensation to synthesize α, β-unsaturated carboxylic acid. The good results showed that [Bmim]BF4 and [Bpy]BF4 were efficient media for Doebner condensation, which could be recycled easily. The highest yields could reach 93% and 90% in [Bmim]BF4 and [Bpy]BF4, respectively.

Poly Ethylene Glycols as Efficient Media for the Synthesis of <i>β</i>-Nitro Styrenes from <i>α</i>, <i>β</i>-Unsaturated Carboxylic Acids and Metal Nitrates under Conventional and Non-Conventional Conditions

Poly ethylene glycols (PEG-200, 400, 600, 4000 and 6000) supported reactions were conducted with certain α, β-unsaturated acids in presence of metal nitrates under solvent free (solid state) and mineral acid free conditions. The reactants were ground in a mortar with a pestle for about 30 minutes. The aromatic acids underwent nitro decarboxylation and afforded β-nitro styrene derivatives in very good yield while α, β-unsaturated aliphatic carboxylic acids gave corresponding nitro derivatives. Addition of PEG accelerated rate of the reaction enormously. Reaction times substantially decreased from several hours to few minutes followed by highly significant increase in the product yield. Among the several PEGs PEG-300 has been found to be much more effective than other PEGs.

Synthesis,thermal decomposition and crystal structure of copper(Ⅱ)α,β-unsaturated carboxylate with urea

A detailed synthesis is described for binuclear cage ternary complexes Cu2A4 [（NH2）2CO]2, where A = CH2 =CH—COO- and CH2 =C（CH3）—COO-. Elemental analysis and thermal analysis have been investigated. The molecular structure of Cu2 （CH2 = CH—COO）4[（NH2）2CO]2 was determined by single crystal X-ray diffraction. The material forms blue crystal with tetragronal symmetry, space group P42/n, a = b = 1. 239 35（6） nm, c = 1. 398 05 （16） nm, Z = 4. There exists, a magnetic exchange interaction between the two paramagnetic Cu atoms. The Cu—Cu bond length is 0.260 94 nm.

Syntheses,characterization,crystal structure and magnetic properties of copper(Ⅱ) α,β-unsaturated carboxylate complexes with trimethyl phosphate

Two ternary complexes Cu2A4[OP(OCH3)3]2 (A represents CH2=CH-COO- and CH2=C(CH3)-COO-) have been synthesized, and elemental analyses, IR, ESR, electronic reflectance spectra and magnetic studies were carried out. The single crystal X-ray diffraction shows that Cu2[CH2=C(CH3)-COO]4[OP(OCH3)3]2 is triclinic, with space group P1, a = 1.05128(13), b = 1.7559(5), c = 1.94479(3) nm, α =91.263(14)°,(β = 102.559(6)°,γ= 106.339(13)°, Z = 4 and R = 0.0668. Two copper(Ⅱ) atoms are bridged by four (a-methacrylate groups, and each copper(Ⅱ) atom is coordinated with a trimethyl phosphate molecule in the axial position, forming a distorted square pyramidal configuration. The symmetric center is between the two copper(Ⅱ) atoms, and the Cu-Cu bond distance is 0.26098(6) nm. The Cu-Cu distance and magnetic studies suggest that there exist anti-ferromagnetic interactions between the two copper(Ⅱ) atoms.

Corrosion inhibition of α,β-unsaturated carbonyl compounds on steel in acid medium

Corrosion inhibition of three α,β-unsaturated carbonyl compounds on N80 steel at high temperature and in concentrated acid medium was evaluated, and the inhibition mechanism was investigated. The results proved that both cinnamaldehyde and benzalacetone had an evident anticorrosion effect and could reduce the corrosion of steel effectively in acid medium, α,β-unsaturated carbonyl compounds with a benzene ring structure had good adsorption on steel surface. The experiments proved that polymerization of α,β-unsaturated carbonyl compounds on the steel surface at a high temperature and in concentrated acid medium resulted in a good corrosion inhibiting effect, which was attributed to the structures of α,β-unsaturated carbonyl compounds.

Gallium trichloride-catalyzed conjugate addition of indole and pyrrole to α,β-unsaturated ketones in aqueous media

Michael addition of indole and pyrrole to a variety of α, β-unsaturated ketones was efficiently promoted by a catalytic amount of GaCl3 in aqueous media to afford the corresponding products in good to excellent yields.

Synthesis of α,β-Unsaturated Ketones using Potassium fluoridealumina Catalyst by Microwave Irradiation

Microwave irradiation can accelerate the rate of the synthetic reaction of α,β-unsaturated ketones by using KF-Al2O3 as catalyst. The rate enhancement of the reaction is 360-860 fold.

Two new α,β-unsaturated butyrolactone derivatives from Pleione bulbocodioides

Two new α,β-unsaturated butyrolactone derivatives, 4-(4″-hydroxybenzyl)-3-(3′-hydroxy-phenethyl)furan-2(5H)-one (1) and 3-(3′-hydroxyphenethyl)furan-2(5H)-one (2), together with one known phenolic compound (3), were isolated from the tubers of Pleione bulbocodioides (Franch.) Rolfe. Their structures were elucidated by analysis of spectroscopic data.

Methanol as hydrogen source: Chemoselective transfer hydrogenation of α,β-unsaturated ketones with a rhodacycle

Methanol is a safe, economic and easy-to-handle hydrogen source. It has rarely been used in transfer hydrogenation reactions, however. We herein report that a cyclometalated rhodium complex, rhodacycle, catalyzes highly chemoselective hydrogenation of α,β-unsaturated ketones with methanol as the hydrogen source. A wide variety of chalcones, styryl methyl ketones and vinyl methyl ketones, including sterically demanding ones, were reduced to the saturated ketones in refluxing methanol in a short reaction time, with no need for inter gas protection, and no reduction of the carbonyl moieties was observed. The catalysis described provides a practically easy and operationally safe method for the reduction of olefinic bonds in α,β-unsaturated ketone compounds.

Nickel (Ⅱ) Complex Catalyzed Conjugate Addition Reaction of Functionalised Organozinc Reagents to α,β -Unsaturated Esters

Functionalized organozinc reagents can easily under 1, 4-addition reaction withunsaturated esters in the presence of catalytic amount of Ni (acac)_2 and tertiary ammes under verymild conditions to give the products in excellent yields.

Addition of Organosamarium Reagents toα, β-Unsaturated Esters

Allylsamarium bromide reacts with Q, 6 -unsaturated esters and a -alkyloxy carbonyl α, β-unsaturated esters to give l,2-addition and 1 .4-addition products respectively.

Cyclization Reaction of α-Triazolyl-α, β-unsaturated Ketones with Phenyl hydrazine

The reaction of α-triazolyl-α, β-unsaturated ketones with phenyl hydrazine was studied. The result indicated that cyclization took place and new heterocyclic compounds of substituted 4,5-2H-pyrazoles were obtained, whose structures and conformation were characterized by 1H NMR, IR, MS, elemental analysis and X-ray diffraction.

Stereoselective Addition of N-Alkylhydroxylamines to α,β-Unsaturated Nitro Compounds

N-Alkylhydroxylamines have been shown to undergo a stereospecific cis addition to 1-phenyl-2 -nitropropene compounds, whereas the corresponding O-alkylhydroxylamines give no diastereoselectivity. The concerted addition mechanism was provided to explain the difference.

Conjugate Addition Reactions of Functionalized Organozinc-copper Reagents to α,β-Unsaturated Esters

Functionalized organozinc reagents can easily conduct 1,4-addition reaction with unsaturated esters in the presence of Cu(OAc)2 and LiCl under very Anld conditions to give the products in excellent yields.

Organocatalyzed Highly Efficient Michael Addition of Malonate Derivatives to α,β-Unsaturated Ketones Using Chiral Schiff Bases

An efficient enantioselective Michael addition of ethyl-2-cyanoacetate and diethyl malonate to α,β-unsaturated ketones catalyzed by a simple chiral Schiff base, and products were obtained in good yields at room temperature.

Ceric Ammonium Nitrate-mediated Oxidative Cycloaddition of 1,3-Dicarbonyls to β-Aryl-α, β-unsaturated Ketones

Regio and stereoselective synthesis of substituted dihydrofurans were accomplished by eeric ammonium nitrate mediated oxidative cycloaddition of 1,3-dicarbonyls to β-aryl-α,β-unsaturated ketones in moderate yields.

A New Method for the Transformation of Alkenes intoα, β-Unsaturated Ketones via Cycloaddition with Dichloroketene

A new synthetic method is described here to obtain α, β-unsaturated ketones through alkenes through a sequence involving f (1) cycloaddition of alkenes with dichloroketene, (2) dechlorination of adducts, (3)acidpromoted ring-opening isomerization ofcyclobutanones in CF3 CO2H.

Michael Additions of Activated Methylene Compounds to α,β-Unsaturated Esters Promoted by Samarium (Ⅲ) Iodide

Promoted by SmI3 β -diketones， β-ketoesters and α -cyano esters were added to α,β -unsaturated esters to form δ-carbonyl esters in mild conditions in moderate to good yields.