Harnessing Cooperative Energy Transfer and Hydrogen Atom Transfer for Direct Nitrogenations of Non‐Activated Alkanes
Open Access
- 28 November 2025
- journal article
- Published by Wiley in Angewandte Chemie International Edition
- Vol. 65 (3) , e18795
Abstract
While important progress has been achieved recently on direct functionalization of alkanes via photocatalytic methods, direct amination of aliphatic compounds remains a great challenge. Herein we report a conceptually new strategy towards direct conversion of hydrocarbons into amines, based on in situ generation of nitrene radical. Energy transfer between thioxanthone (TXO) photocatalyst and iminoiodinane furnishes the triplet nitrene radical, able to undergo HAT reaction promoting alkane activation and subsequent C─N bond formation step. The user‐friendly nature of the metal‐free transformation, along with mild reaction conditions further highlight the sustainability of this scalable process delivering a diversity of cycloalkylamines. Combined experimental and computational mechanistic studies support the unusual reaction mechanism.Keywords
This publication has 73 references indexed in Scilit:
- Homogeneous Iron Catalyzed C−H AminationChemCatChem, 2024
- Preparative Scale Applications of C−H Activation in Medicinal ChemistryAngewandte Chemie International Edition, 2023
- Visible Light‐Enhanced C−H Amination of Cyclic Ethers with IminoiodinanesAdvanced Synthesis & Catalysis, 2022
- Catalytic Enantioselective Methylene C(sp3)−H Amidation of 8‐Alkylquinolines Using a Cp*RhIII/Chiral Carboxylic Acid SystemAngewandte Chemie International Edition, 2019
- Enantioselective C(sp3)–H Amidation of Thioamides Catalyzed by a CobaltIII/Chiral Carboxylic Acid Hybrid SystemAngewandte Chemie International Edition, 2018
- Photoactivated N‐Acyliminoiodinanes Applied to Amination: an ortho‐Methoxymethyl Group Stabilizes Reactive PrecursorsAngewandte Chemie International Edition, 2017
- Spin‐Selective Generation of Triplet Nitrenes: Olefin Aziridination through Visible‐Light Photosensitization of AzidoformatesAngewandte Chemie International Edition, 2016
- Synthesis of 1,3‐Diamines Through Rhodium‐Catalyzed C-H InsertionAngewandte Chemie International Edition, 2009
- Copper–Nitrene Complexes in Catalytic C-H AminationAngewandte Chemie International Edition, 2008
- Rhodium(II)-catalyzed aziridinations and CH insertions with [N-(p-nitrobenzenesulfonyl)imino]phenyliodinaneJournal of Physical Organic Chemistry, 1996