Photoredox‐Catalyzed α−C−H Monoalkylation of Symmetric Polyols in the Presence of CO2

Author:

Archer Gaétan1,Meyrelles Ricardo234,Eder Isabel2,Kovács Nóra2,Maryasin Boris23ORCID,Médebielle Maurice1ORCID,Merad Jérémy1ORCID

Affiliation:

1. ICBMS UMR 5246 Univ Lyon Université Lyon 1 CNRS INSA CPE-Lyon ICBMS 1 rue Victor Grignard 69622 Villeurbanne France

2. Institute of Theoretical Chemistry University of Vienna Währinger Straße 17 1090 Vienna Austria

3. Institute of Organic Chemistry University of Vienna Währinger Straße 38 1090 Vienna Austria

4. Vienna Doctoral School in Chemistry University of Vienna Währinger Straße 42 1090 Vienna Austria

Abstract

AbstractAchieving 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.

Funder

Agence Nationale de la Recherche

Publisher

Wiley

Subject

General Chemistry,Catalysis

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