Chiral counteranion controlled chemoselectivity in gold catalysed hydroamination/enantioselective formal 1,3-allylic alcohol isomerisation of β-amino-1,4-enynols

A synthetic method for the preparation of 1,8-dihydroindeno[2,1-b]pyrroles and pyrrol-2-yl methanols in an enantioselective manner that relies on chiral gold(I)-catalysed reactions β-amino-1,4-enynols is described. divergence product selectivity was achieved by exploiting electrostatic interactions between counteranion metal catalyst substrate. With a gold(I) complex containing N-triflyl phosphoramide-based counteranion, tandem dehydrative Nazarov-type electrocyclisation/hydroamination substrate found to selectively occur afford indeno-fused pyrrole adduct. In contrast, changing phosphate-based observed result hydroamination/enantioselective formal 1,3-allylic alcohol isomerisation cascade pathway give 1H-pyrrole derivative.