Preparation and Diels-Alder reactions of 1'-heterosubsituted vinylimidazoles

A Diels-Alder/rearrangement sequence has been pursued in our lab en route to a number of oroidin dimers. In order to access the fully substituted core of these molecules, 1',2'-disubstituted 4-vinylimidazoles were required as dienes. The preparation of a series of a 4-vinylimidazoles containing substituents on the vinyl moiety via hydroalumination/electrophilic trapping or hydrosilylation are described. These derivatives undergo Diels-Alder reactions with N-phenylmaleimide to provide the tetrahydrobenzimidazole derivatives. The cycloadducts derived from halosubstituted systems generally undergo elimination, leading to the corresponding dihydrobenzimidazole, whereas the silyl and stannyl derivatives provide the corresponding 4-substituted tetrahydrobenzimidazole.