Bending Enamine Patterns of Stabilized Pentalenes into "Polymethine Ylides"

Abstract

We report the synthesis and structural study of 2-substituted 1,3-bis(dimethylamino)pentalenes. The two electrons donating substituents shift the formally anti-aromatic pattern toward more suitable polarized structures. A subtle steric trade-off can result either in planar cyclopentadienyl vinamidiniums or in distorted structures featuring a pyramidalized ylidic carbon adjacent to a stabilized π-conjugated iminium (polymethine). This latter pattern mimics a postulated activated distorted geometry for key Breslow intermediates in the active site of thiamine-dependent enzymes. It highlights how the energetic drive to avoid anti-aromaticity can be used to access models for unconventional distorted conformations of organic molecules.