The proton catalyzed reaction of methyldiazoacetate and benzaldehyde resulting in the formation of b-ketoesters and 3-hydroxyacrylates has been investigated by means of DFT/B3LYP calculations. Experimentally this reaction is performed using HBF4 Et2O as the catalyst and CH2Cl2 as the solvent. Several mechanistic pathways involving 1,2-migration of phenyl-, H-, and OH-substituents have been cons...

It has been shown for the first time that relatively electron deficient triazolium pre-catalysts promote (at low loadings in the presence of base) highly chemoselective crossed acyloin condensation reactions between aldehydes and a-ketoesters to afford densely functionalized products incorporating a quaternary stereocentre of considerable synthetic potential. Hydroacylation pathways which have ...

A simple, efficient procedure for the one-pot Biginelli condensation reaction of aldehydes, beta-ketoesters and urea or thiourea employing copper(II) sulfamate as a novel catalyst is described. Compared to the classical Biginelli reaction conditions, the present method has the advantages of good yields, short reaction times and experimental simplicity.

An efficient catalytic asymmetric hetero-ene reaction of 5-methyleneoxazolines with 1,2-dicarbonyl compounds (including α-ketoesters and glyoxal derivatives) was realized using Ni(II)-N,N'-dioxide complexes as the catalysts. It provides a rapid, high yielding (up to 99%) route for the preparation of 2,5-disubstituted oxazole derivatives in a highly enantioenriched form (up to >99% ee) under mil...

The air and moisture stable fluoroiodane 8, readily prepared on a 6 g scale by nucleophilic fluorination of the hydroxyiodane 7 with TREAT-HF, has been used as an electrophilic fluorinating reagent for the first time to monofluorinate 1,3-ketoesters and difluorinate 1,3-diketones in good isolated yields.