Reactions of 3а,6a-diaza-1,4-diphosphapentalene with activated acetylenes

Abstract

The reaction of cyclohexane-annulated 3 a,6a-diaza-1,4-diphosphapentalene (DDP) with di-tert-butyl acetylenedicarboxylate (DBAD) affords the 1,3-dipolar cycloaddition product of the acetylene moiety to the phosphorus and sp²-carbon atoms of DDP in 90% yield. No individual products were isolated in the reaction of DDP with dimethyl acetylenedicarboxylate (DMAD). In the three-component DDP–DMAD–carbazole system (1: 2: 1), a product was generated in 73% yield via successive reactions, including the 1(P),3(C)-dipolar cycloaddition of DMAD to DDP, the addition of the second equivalent of DMAD to the three-coordinate phosphorus atom of the intermediate, and the NH addition of carbazole at the unsaturated C=C bond of the second DMAD moiety. The structures of the reaction products were established by X-ray diffraction.