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Updated: Jun 4, 2025

A Two-Step Protocol for Umpolung Functionalization of Ketones Via Enolonium Species
Published on: August 16, 2018
Electroredox N-Heterocyclic Carbene-Catalyzed Enantioselective (3 + 3) Annulation of Enals with 2-Naphthols
Vikas Kale1, Sayan Shee2, Shiv Dutt1
1Department of Chemistry, Indian Institute of Technology Ropar, Rupnagar, Punjab 140001, India.
Abstract:
Developing asymmetric transformations using electroredox and N-heterocyclic carbene (NHC)-catalyzed radical pathways is still desirable and challenging. Herein, we report an iodide-promoted β-carbon activation (LUMO-lowering process) of enals via electroredox carbene catalysis coupled with a hydrogen evolution reaction (HER). This strategy offers an environmentally friendly and sustainable route for rapidly assembling synthetically useful chiral naphthopyran-3-one in good to excellent yield and enantioselectivity using traceless electrons as inexpensive and greener oxidants. The mechanistic studies and cyclic voltammetry suggest that the reaction proceeds via direct single electron transfer (SET) of the in situ-generated Breslow intermediate.
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