Search results for "Cyclohexenone"
showing 2 items of 2 documents
Installation of Amine Moieties into a Polycyclic Anodic Product Derived from 2,4-Dimethylphenol
2011
When 2,4-dimethylphenol is anodically treated, a dehydrotetramer with four contiguous stereocentres is readily obtained on a multi-gram scale. The substitution of a 2,4-dimethyl-phenoxy fragment by several amines was demonstrated, and the best results were obtained with primary amines. Optically pure α-chiral aliphatic amines yield diastereomeric mixtures that can be separated in most cases. The basic amine causes a partial hemiketal-opening of the bisbenzofuran moiety leading to an equilibrium within an α,β-unsaturated cyclohexenone. This dynamic behaviour occurs on the time scale of NMR spectroscopy and is also found by X-ray analysis providing a consistent picture.
Lewis Acid Mediated Domino Reaction between 2-Cyclohexenone and Methyl Azide - A DFT Study
2005
We have studied the Lewis acid mediated domino reaction between 2-cyclohexenone and methyl azide at the B3LYP/6-31G* and B3LYP/6-31+G**//B3LYP/6-31G* levels of theory. A complete survey of the potential energy surface is presented, and the structures of the stationary points and the corresponding molecular mechanism are discussed. The calculations suggest that the product, a cyclopentanone derivative, is formed by means of a domino process that comprises three consecutive reactions. The first and rate-limiting step is a concerted 1,3-dipolar cycloaddition between the Lewis acid coordinated cyclohexenone and methyl azide that yields the corresponding bicyclic 1,2,3-triazoline. The second rea…