Ambiphilic molecules for trapping reactive intermediates: interrupted Nazarov reaction of allenyl vinyl ketones with Me2PCH2AlMe2

The addition of the ambiphilic molecule Me2AlCH2PMe2 (1) to the allenyl vinyl ketone 2 gave a trapped Nazarov reaction product. Under kinetic control, the addition of the phosphine was on the methylated carbon, contrary to expected steric and electronic considerations. Computational data pointed to hydrogen bonding between the phosphine and the methyl group guiding the regiochemistry of this reaction. This product rearranged to provide the expected, regioisomeric Nazarov product. With additional 1 this compound yielded a Michael-addition product via a retro-Nazarov process.