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. .

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.

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.

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.

Stereoselective cycloaddition of N-acyliminium cations withα,β-unsaturated ketones and esters

The cycloaddition of N-acyliminium cations with some deactivated alkenes such as α,β-unsaturate ketones and esters has been investigated. In most cases, the N-acyliminium cations produced from 3-hydroxy-2-arylisoindol-1-ones in the presence of BFa.OEt2 could be reacted with α,β-unsaturated ketones and esters to afford stereoselectively the cycloaddition products 6-acylisoindolo[2,1- a]quinolin-11-ones in moderate to high yields. C 2009 Wei Zhang. Published by Elsevier B.V, on behalf of Chinese Chemical Society. All rights reserved.

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.

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.

Ytterbium triflate hydrate catalyzed Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds

Catalyzed by ytterbium（III） triflate hydrate [Yb（OTf）3.xH20], the Michael addition and cyclocondensation of α,β-unsaturated ketones with active methylene compounds to afford the 1,4-adducts and benzo[b]pyran derivatives, respectively were studied.

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.

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.

Facile and Green Synthesis of α,β-Unsaturated Ketone Catalyzed by Air-Stable Organobismuth Complex

Air-stable cationic organobismuth complexes (2-5) possessing both acidic and basic characters were synthesized. The catalyst system that comprises an air-stable bifunctional Lewis acidic/basic organobismuth complex and [Bmim]BF4 showed high catalytic activity, diastereoselec-tivity, stability, and reusability in the one-pot synthesis of (E)-α,β-unsaturat-ed ketones through highly selective crossed-condensation of ketones and aldehydes. Through switching the reaction from homogeneous to heterogeneous, the system shows facile separation ability and facile reusability.

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.

Visible-Light-Induced[4+1]Cyclization-Aromatization of Acylsilanes andα,β-Unsaturated Ketones

Herein we report the first[4+1]cyclization-aromatization reaction of acylsilanes andα,β-unsaturated ketones.The unprecedented visible-light-induced reaction proceeded through mild conditions without addition of any catalyst or additive,affording a variety of furans with broad substrate scope and good functional-group tolerance.The synthetic utility of the method was demonstrated by various downstream transformations of the otherwise difficult-to-access sulfone-containing silyl furans.The mechanism study reveals that 1,4-diketones are not likely to be the intermediates of the reaction.

Enantioselective[3 t 2]cycloadditions of terminal allenoates withβ-sulfonyl-α,β-unsaturated ketones

A highly efficient and mild method for[3 t 2]cycloaddition ofβ-sulfonyl-α,β-unsaturated ketones with terminal allenoates was well-explored and developed.The reactions were successfully performed by applying multifunctional chiral phosphine P6 which was screened from eight chiral phosphorus reagents to finally result in a variety of enantioenriched sulfone-substituted cyclopentenes with two chiral centers(up to 81%yield with 94%ee).Moreover,2.5 mol%catalytic equivalents were proved to be feasible when this reaction was performed on a 10 mmol scale.

Enantioselective Hydrogenation of α,β-Unsaturated Cyclic Ketones by Double Asymmetric Induction Preparation of (R)-Muscone

By ketal formation with chiral glycols like methyl or ethyl ester of tartaric acid,hydrogenation of ketals from the correspondingα,β-unsaturated 15-membered cyclic ketone produces (R)-muscone in good chemical and optical yield in the presence of chiral catalysts

Efficient synthesis of terminal α,β-unsaturated ketones as the intermediates of the proteasome epoxyketone inhibitors via Weinreb amide

Peptidyl epoxyketones were potential antitumor agents due to their 20S proteasome inhibitory activities. Based on their structures and special inhibitory mechanism, a series of compounds were designed by linking the epoxyketone moiety （the Cterminal pharmacophore） and the peptide backbones. To make these compounds, we used a novel method to prepare the terminal α,β-unsaturated ketone, the crucial intermediate, from Weinreb amide with satisfactory yield （62%-65%）.

Conjugate Addition of Indoles to α, β-Unsaturated Ketones （Chalcones） Catalyzed by KHSO4 under Ultrasonic Conditions

Conjugate addition of indoles to a variety of α,β-unsaturated ketones （chalcones） mediated by a catalytic amount of KHSO4 at room temperature under ultrasonic conditions to afford the corresponding Michael adducts in good to excellent yields was reported.

Asymmetric Hydrogenation of Tetrasubstituted α,β-Unsaturated Ketones:Access to Chiral 2-Substituted Cyclopentyl Aryl Ketones

Asymmetric hydrogenation of tetrasubstituted alkenes is an important but challenging research topic.Herein,we report an efficient iridium-catalyzed asymmetric hydrogenation of tetrasubstituted α,β-unsaturated ketones for the synthesis of chiral 2-substituted cyclopentyl aryl ketones,an important chiral structural motif for the preparation of chiral pharmaceuticals and bioactive molecules.The reaction proceeded very well with good functional group compatibility and delivered the hydrogenated products in high yields and stereoselectivities(up to 99% yield,>20:1 dr and 99%ee).In addition,the reaction could be carried out on a gram-scale,and all four stereoisomers of the hydrogenated products bearing two contiguous stereocenters were obtained.Furthermore,the hydrogenated product can be transformed into the ERβ agonist Erteberel,and the reaction pathway was also studied via deuterium-labelling experiments.

Helical Poly(α,β-unsaturated ketone)with Bulky Pendant of Binaphthyl from Anionic Polymerization of(−)-Menthyl(S)-6'-Acrylyl-2'-methyloxy-1,1'-binaphthalene-2-carboxylate

(−)-Menthyl(S)-6'-acrylyl-2'-methyloxy-1,1'-binaphthalene-2-carboxylate(3)was synthesized and anionically polymerized using n-BuLi as an initiator in toluene.The monomer 3 was levorotatory and had an[α]_(D)^(25)value of−72.4,but its corresponding polymer poly-3 was dextrorotatory and showed an[α]_(D)^(25)value of+162.0.Poly-3 was confirmed to exist in the form of one-handed helical structure in solution by means of comparing the specific optical rotation and the CD spectra with that of 3 and the model compounds such as(−)-menthyl(S)-6'-propionyl-2'-methyloxy-1,1'-binaphthalene-2-carboxylate 2b and(−)-menthyl(S)-6'-heptanoyl-2'-methyloxy-1,1'-binaphthalene-2-carboxylate 2c.This conclusion was also confirmed by the fact that the g-value of poly-3 is about 11 times of that of monomer 3.

Catalytic conjugate addition of indole toα,β-unsaturated ketones by Co(ClO_4)-2·6H_2O/bis-Schiff base complexes

Co（ClO_4））_2·6H_2O/bis-Schiff base complexes promoted the conjugate addition of indole toα,β-unsaturated ketones under mild conditions,giving the corresponding addition products with high yields.And the complex has been characterized with XRD and IR.