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

Lorenzo Carli, Anyawan Tapdara, Jianwen Jin, Yichao Zhao, Philip Wai Hong Chan

Research output: Contribution to journalArticleResearchpeer-review

Abstract

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

Original languageEnglish
Article number100043
Number of pages7
JournalTetrahedron Chem
Volume7
DOIs
Publication statusPublished - Aug 2023

Keywords

  • Asymmetric catalysis
  • Cycloisomerisation
  • Gold
  • N-Heterocyclic synthesis
  • Synthetic methods

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