Synthesis, Tautomerism, and Catalysis

A restricted Hartree-Fock study of formation of Schiff base (A-[(Z)-furan-2-ylmethylidene]-4-methoxyaniline) from aromatic amine and furaldehyde has revealed that an auxiliary water molecule enables proton transfer in the carbinolamine-forming 

An unprecedented highly enantioselective catalytic isomerism of trifluoromethylim-ines (2) has been promoted by a chiral organic catalyst (1) and thereby provided a new approach to optically active alkyl and aryl trifluoromethylated amines (3).  

Infrared spectra and structures have been reported for nitrile imines generated pho-tochemically and thermally in Ar matrices at cryogenic temperature. The results are consistent with theoretical predictions, and the isomerization of both propargylic and allenic forms to the corresponding carbodiimides could be reversed by flash vacuum 

The kinetics and thermodynamics of the formation of E and Zenamines between aldehydes with a-stereocentres and pyrrolidine-based catalysts that lack an acidic proton have been studied as a guide to the probable diastereo- and enantio-selection towards electrophiles when introduced.  

Fifty years of established views of the Ugi reaction have been challenged by results of a theoretical study which suggests, for example, that the intermediate imine is not in equilibrium with its isocyanide adduct. An asymmetric three-component Ugi reaction has applied chiral cyclic imines in synthesis of morpholino- or piperazine-keto-carboxamide derivatives.  

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