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- Title
Photoredox‐Catalyzed α−C−H Monoalkylation of Symmetric Polyols in the Presence of CO<sub>2</sub>.
- Authors
Archer, Gaétan; Meyrelles, Ricardo; Eder, Isabel; Kovács, Nóra; Maryasin, Boris; Médebielle, Maurice; Merad, Jérémy
- Abstract
Achieving the selective modification of symmetric poly‐hydroxylated compounds presents a significant challenge due to the presence of identical active sites. Herein, we address this challenge through the design of a ternary catalytic system that includes a photoredox catalyst, a hydrogen atom transfer promotor and a carbonation catalyst. This catalytic system enables the reversible carbonation of acyclic polyols under CO2 atmosphere, which modulates the reactivity of its distinct C−H bonds toward hydrogen atom transfers. An exquisite selectivity for the monoalkylation is achieved in a variety of unprotected light polyols, yielding valuable building blocks in short reaction times. Mechanistic and computational studies demonstrate that the formation of an intramolecular hydrogen bond between the transient carbonate and the free alcohol is pivotal for the kinetic and thermodynamic activation of a specific alcohol.
- Subjects
ABSTRACTION reactions; ATMOSPHERIC carbon dioxide; POLYOLS; CARBONATION (Chemistry); HYDROGEN bonding; TERNARY system
- Publication
Angewandte Chemie, 2024, Vol 136, Issue 6, p1
- ISSN
0044-8249
- Publication type
Article
- DOI
10.1002/ange.202315329