CONTROLLED ACCELERATION AND INHIBITION OF BERGMAN CYCLIZATION BY METAL CHLORIDES

The Bergman cyclization has been the subject of renewed interest with the discovery of naturally occurring enediyne-based antitumor agents t hat cleave DNA by means of an aromatic diradical. These natural substr ates have a means to trigger this cycloaromatization process. Control of this reaction by substrate modification would allow aromatic diradi cals to be generated selectively. in the studies presented here it is disclosed that the Bergman cyclization of 1,2-bis(diphenyl phosphinoet hynyl)benzene was accelerated by a factor of >30,000 by the addition o f palladium(II) chloride or platinum(II) chloride and was inhibited by the addition of mercury(II) chloride.