Redox-Neutral Multicatalytic Cerium Photoredox-Enabled Cleavage of O–H Bearing Substrates

06 December 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

The need for synthetic methodologies capable of rapidly altering molecular structure are in high demand. Most existing methods to modify scaffolds rely on net exothermicity to drive the desired transformation. We sought to develop a general strategy for the cleavage of C–C bonds beta to hydroxyl groups independent of inherent substrate strain. To this end we have applied a multicatalytic cerium photoredox-based system capable of activating O–H bonds in lactols to deliver formate esters. The same system is also capable of effecting hydrodecarboxylation and hydrodecarbonylation reactions. Initial mechanistic probes demonstrate atomic chlorine (Cl•) is generated under the reaction conditions, but substrate activation through cerium-alkoxides or -carboxylates cannot be ruled out.

Keywords

catalysis • photoredox • C–C bond fragmentation • cerium • radicals

Supplementary materials

Title
Description
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Title
Redox-Neutral Multicatalytic Cerium Photoredox-Enabled Cleavage of O–H Bearing Substrates
Description
Supporting Information. Preparation and characterization of all new materials
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