We present an easy method for the synthesis of β-ketoesters starting from various carbocyclic and heterocyclic carboxylic acids and esters. The β-ketoester side-chain was introduced by a sequence involving α-deprotonation and quenching with CO2, conversion to the corresponding acid chloride and subsequent chain elongation using deprotonated ethyl acetate.

Imidazolium-based ionic liquids (ILs) serve both as recyclable reaction media and as precatalysts for the N-heterocyclic carbene-catalyzed conjugate addition of α,β-unsaturated aldehydes to chalcones. The reaction produces a broad scope of 1,6-ketoesters incorporating an anti-diphenyl moiety in high yields and with high stereoselectivity. In recycling experiments, the IL can be reused up to fiv...

The fragmentation reaction of differently functionalized [2.2.2]- and [2.2.1]bicyclic systems that leads to substituted five membered heterocycles and five/six membered carbocycles is broadly studied. This reaction is carried out through a retro-Dieckmann-type condensation on strained [2.2.1]bicyclic β-ketosulfones and their counterparts β-ketoesters under very mild catalytic acid or basic cond...

Reaction of Ti(OiPr)(4) with various bis(β-diketones) and bis(β-ketoesters) (LH(2)) results in the formation of dimeric complexes [Ti(OiPr)(2)L](2), where each metal centre is coordinated by two terminal OiPr ligands and two bridging β-diketonate or β-ketoesterate groups (L). Macrocycles containing two M(OiPr)(2) moieties are thus formed. Reaction of Zr(OiPr)(4) with the same bis(β-diketones) a...

The palladium-catalyzed decarboxylative allylic alkylation of diastereomeric β-ketoesters derived from 4-tert-butylcyclohexanone is described. These experiments were performed to elucidate our understanding of stereoablative enantioconvergent catalysis. A detailed analysis of the product distribution, including stereochemical outcome of the products, is included. These studies also reveal an in...

The first catalytic asymmetric pseudo five-component (AB(2)C(2) type) reaction is reported. A spirocyclic chiral phosphoric acid catalyzed one-pot multicomponent reaction of aromatic aldehydes, anilines and β-ketoesters and afforded highly functionalized enantioenriched tetrahydropyridines with high levels of stereocontrol.

The visible-light-driven, phase-transfer-catalyzed, enantioselective perfluoroalkylation and trifluoromethylation of cyclic β-ketoesters is described. The photo-organocatalytic process, which occurs at ambient temperature and under visible light illumination, is triggered by the photochemical activity of in situ-generated electron donor-acceptor complexes, arising from the association of chiral...

One pot syntheses of furan, thiophene, and pyrrole were accomplished by oxidative deacetylation using Mn(III)/Co(II) catalysts and the Paal-Knorr reaction from 1,5-dicarbonyl compounds, which are prepared from the conjugate addition of ethyl acetoacetate to α,β-unsaturated carbonyl compounds. The oxidative deacetylation and reductive cyclization of β-ketoesters derived from ethyl acetoacetate a...