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HFIP-Promoted Regioselective Hydrofunctionalization of Enamides and N ‑Vinyl Azoles

Title: HFIP-Promoted Regioselective Hydrofunctionalization of Enamides and N ‑Vinyl Azoles
Authors: Susanta Patra; Satyajit Samanta; Vishal Talukdar; Parthasarathi Das
Publication Year: 2025
Subject Terms: Biophysics; Biochemistry; Genetics; Evolutionary Biology; Computational Biology; Biological Sciences not elsewhere classified; Chemical Sciences not elsewhere classified; iminium carbocation intermediate; facilitating nucleophile generation; broad substrate compatibility; >‑ vinyl azoles; >- vinyl azoles; selective hydrofunctionalization pathway; diverse c –; promoted regioselective hydrofunctionalization; >- free indoles; c – n; c –; intermolecular hydrofunctionalization; regioselective method; n
Description: An efficient and regioselective method for the intermolecular hydrofunctionalization of enamides and N -vinyl azoles has been developed, enabling the formation of diverse C–S, C–O, C–N, and C–C bonds. This transition-metal-free, additive-free, and Brønsted acid-free protocol employs hexafluoroisopropanol (HFIP) as the sole reagent, which plays a dual role: formation of iminium carbocation intermediate and facilitating nucleophile generation through its hydrogen-bonding network. The reaction demonstrates exceptional substrate versatility, accommodating thiophenols, alcohols, heterocyclic amines, as well as NH -free indoles, pyrroles, and carbazoles as nucleophiles, proceeding via a Markovnikov-selective hydrofunctionalization pathway. The protocol is general and simple with broad substrate compatibility.
Document Type: article in journal/newspaper
Language: unknown
DOI: 10.1021/acs.joc.5c00378.s001
Availability: https://doi.org/10.1021/acs.joc.5c00378.s001; https://figshare.com/articles/journal_contribution/HFIP-Promoted_Regioselective_Hydrofunctionalization_of_Enamides_and_i_N_i_Vinyl_Azoles/28892863
Rights: CC BY-NC 4.0
Accession Number: edsbas.7E69C663
Database: BASE