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Relevant academic research and scientific papers

Formation of Bicyclic Cyclopentenone Derivatives by Robinson-Type Annulation of Cyclic β-Oxoesters Containing a 1,4-Diketone Moiety

Robinson-type cyclopentannulations of cyclic β-oxoesters possessing a 1,4-diketone moiety are accomplished under four different Bronsted basic reaction conditions. Using pyrrolidine/acetic acid in DMSO, an oxohexahydrocyclopenta[ a ]indene (42%) and an N

MULTI-STEP CATALYSIS FOR THE OXIDATION OF OLEFINS TO KETONES BY MOLECULAR OXYGEN IN CHLORIDE FREE MEDIA

A multi-step catalytic system consisting of Pd(II)/Pd(0) - benzoquinone/hydroquinone - Fe(Pc)ox/Fe(Pc) was utilized to achieve a mild and selective aerobic oxidation of terminal olefins to methyl ketones in chloride free media.

Convenient Wacker oxidations with substoichiometric cupric acetate

A modification of the Wacker oxidation of terminal olefins to methyl ketones using substoichiometric amounts of Cu(OAc)2 as a redox shuttle reagent is described. The modified procedure is generally high yielding despite reduced levels of copper salt and convenient. Importantly, in a problematic case, the conditions suppressed acidic hydrolysis during oxidation of substrate (+)-5 containing an acetonide.

Intramolecular Schmidt Reaction of Vinyl Azides with Cyclic Ketones

Cyclic ketones tethered with a vinyl azide group undergo a Schmidt-hydrolysis sequence to give secondary lactams bearing a ketone side chain. Secondary lactams are obtained in a regioselective manner that is not possible in a conventional Schimdt reaction. In addition to the well-documented C-2 nucleophilicity, the N nucleophilicity of vinyl azide disclosed in this work opens a new direction for reaction invention involving vinyl azides.

Synthesis of 1,4-Diketones from β-Oxo Esters and Enol Acetates by Cerium-Catalyzed Oxidative Umpolung Reaction

Cyclic β-oxo esters are converted with enol acetates in a cerium-catalyzed, oxidative Umpolung reaction to furnish 1,4-diketones with up to 95 % yield. Atmospheric oxygen is the oxidant in this process, which can be regarded as ideal from economic and ecological points of view. Further advantages of this new C-C coupling reaction are its operational simplicity and the application of nontoxic and inexpensive CeCl3·7H2O as precatalyst.

Gold-catalyzed synthesis of carbon-bridged medium-sized rings

Bicyclo[m.n.1]alkenone frameworks possessing quaternary carbon centers adjacent to a bridged ketone are frequently found in bioactive natural products. Although several methods have been developed to construct such frameworks, most of them are specific to a particular scaffold. Herein, we report a mild and highly efficient method to generate carbon-bridged frameworks of various sizes using phosphlno gold(I) catalysts.

Electroorganic Synthesis, 58. Synthesis of Substituted Benzoquinones and their Use for Mediated Electrochemical Conversions

Hydroxy- (1a-3a) and hydroxyalkyl-substituted benzoquinones (6a-8a, 27a), suited to be immobilized by esterification with polyacrylic acid, are prepared.Their cathodic reduction potential Ep,c (1) correlates linearly with their substituent constant.The cathodic reduction of dioxygen and the palladium(II)-catalyzed anodic oxidation of alkenes are mediated by the benzoquinones 7b, 8b and 27b, respectively. - Key Words: Benzoquinones, substituted / Cyclic voltammetry / Cathodic dioxygen reduction, mediated / Anodic Wacker oxidation, mediated

THE SYNTHESIS AND CHEMISTRY OF AZOLENINES. PART 18. PREPARATION OF 3-ETHOXYCARBONYL-3H-PYRROLES VIA THE PAAL-KNORR REACTION, AND SIGMATROPIC REARRANGEMENTS INVOLVING COMPETITIVE ESTER MIGRATIONS TO C-2, C-4 AND N.

3H-Pyrrole-3-carboxylic esters (4) have been prepared, in some cases together with isomers (5) and (6) having exocyclic double bonds, by cyclization of suitably substituted 2-ethoxycarbonyl-1,4-diketones (1) with liquid ammonia, followed by dehydration of the isolable 2-hydroxy-3,4-dihydro-2H-pyrrole intermediates (2) and (3) with aluminia in boiling solvents.Prolonged heating in toluene or p-xylene converts the 3H-pyrroles (4) quantitatively into isomeric 4-esters (11) and N-esters (13) of 1H-pyrroles via competitive sigmatropic rearrangements.Isolable intermediate 2H-pyrrole-2-carboxylic esters (12) are converted similarly into the same products, under the same conditions.Detection of 3H-pyrroles (4) as intermediates in the latter reaction demonstrates for the first time the reversibility of the thermal 2H-pyrrole to 3H-pyrrole interconversion.

Multistep electron transfer in palladium-catalyzed aerobic oxidations via a metal macrocycle-quinone system

Selective palladium-catalyzed aerobic conditions of olefins and conjugated dienes with the aid of a metal macrocycle-quinone system have been developed. This involves a multistep electron transfer with three catalysts (Pd(OAc)2, hydroquinone, metal macrocycle). The triple catalytic system was applied to (i) 1 ,4-oxidation of conjugated dienes (1,4-diacetoxylation and 1,4-dialkoxylation), (ii) oxidation of terminal olefins to ketones, and (iii) allylic oxidation of cyclic olefins to 2-alken-1-yl acetates. The reactions occur under very mild conditions, (i) and (ii) at room temperature and (iii) at 60 °C, and are reminiscent of aerobic processes occurring in living organisms. Thus, there is an electron transfer from the substrate to Pd(II) giving Pd(0), followed by another electron transfer from Pd(0) to benzoquinone. The hydroquinone thus formed transfers electrons to the oxidized form of the metal macrocycle, which is reduced. The latter is reoxidized by electron transfer to molecular oxygen. A number of metal macrocycles such as metal(salen) complexes Co(salophen), Co(TPP), and iron phthalocyanine (Fe(Pc)) were tested as oxygen-activating complexes. In the 1,4-diacetoxylation of 1,3-dienes, and in the allylic oxidation, several of these metal macrocycles gave good results. In the 1,4-dialkoxylation of 1,3-dienes and in the oxidation of terminal olefins to ketones, which occur in the presence of a strong acid, only Fe(Pc) survived the reaction conditions.

Mn(III)-PROMOTED ANNULATION OF ENOL ETHERS AND ESTERS TO FUSED OR SPIRO 2-CYCLOPENTENONES

Manganese(III)-promoted addition of various 1,3-dicarbonyl compounds to enol ethers or terminal enol esters, followed by hydrolysis of the resulting adducts and base catalyzed aldol cyclization provides an effective process for the synthesis of a wide ran