Metal-free visible-light carbonylation of alkyl iodides to amides <i>via</i> consecutive photoinduced electron transfer
A visible-light-driven, metal-free carbonylation of unactivated alkyl iodides is reported, enabling the direct synthesis of 35 structurally diverse amides in good to excellent yields. The reaction shows broad functional-group tolerance toward both amines and alkyl iodides, including bioisosteric motifs and complex natural product derivatives, underscoring its potential for late-stage functionalization. Mechanistic investigations combining flash photolysis, spectroelectrochemistry, irradiated thin-layer cyclic voltammetry, and EPR spectroscopy reveal a consecutive photoinduced electron transfer (ConPET) mechanism that diverges from conventional single-photon photoredox catalysis. DFT calculations elucidate the key radical carbonylation steps governing reactivity and selectivity. This sustainable and operationally simple method offers a transition-metal-free approach to carbonylation, expanding the toolbox for highly reducing transformations under mild conditions.
Authors
- Jasmine Hertzog (ORCID: https://orcid.org/0000-0002-7946-1904)
- Christophe Werlé (ORCID: https://orcid.org/0000-0002-2174-2148)
- Fatima Akhssas
- Ibrahim M. Abdellah
- Michaël Badawi (ORCID: https://orcid.org/0000-0002-3504-4180)
- Zakaria Halime (ORCID: https://orcid.org/0000-0003-3080-9727)
- Alexandre Vasseur (ORCID: https://orcid.org/0000-0003-3294-2417)
- Bertrand Vileno
- Guillaume Chu
- Naomi Illi
- Meriem El Malamy
- Philipp Gotico
- Nolwenn Le Breton
- Miguel Ponce-Vargas
Institutions
- Centre National de la Recherche Scientifique (FR)
- Commissariat à l'Énergie Atomique et aux Énergies Alternatives (FR)
- Université Paris-Saclay (FR)
- Institut de Chimie de Strasbourg (FR)
- Institut de Biologie Intégrative de la Cellule (FR)
- Max Planck Institute for Chemical Energy Conversion (DE)
- CEA Paris-Saclay (FR)
- Institut de Chimie Moléculaire et des Matériaux d'Orsay (FR)
- Laboratoire de Chimie et Physique - Approche Multi-échelle des Milieux Complexes
- Laboratoire Lorrain de Chimie Moléculaire (FR)
- Université de Strasbourg (FR)
- Université de Lorraine (FR)
- Université de Reims Champagne-Ardenne (FR)
Publication Details
- Journal
- Chemical Science
- Published
- 2026-01-01
- DOI
- https://doi.org/10.1039/d5sc09778a
- Primary Topic
- Radical Photochemical Reactions
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Agence Nationale de la Recherche
- Max-Planck-Gesellschaft