Work

Controlled Dealkylation of Alkyl Esters With Halide Salts and Application in Tandem‐Catalyzed Protodecarboxylation of Organic Formates

Year: 2026

Type: article

Abstract: ABSTRACT The selective cleavage of the C–O bond of unactivated alkyl esters remains a major challenge to use them as C(sp 3 )‐electrophiles in cross‐coupling chemistry. Here, we report a systematic study on the dealkylation of alkyl formates using iodide salts, revealing the pivotal role of the Lewis acidic countercation (K + , Na + , Li + , Ca 2 + , Mg 2 + , and Al 3 + ) in accelerating C–O bond cleavage. Kinetic analyses demonstrate a seven‐order‐of‐magnitude rate enhancement when replacing LiI with AlI 3 . To highlight the synthetic potential of this finding, we further integrate this reactivity into a tandem catalytic system combining AlI 3 and a ruthenium catalyst, achieving efficient protodecarboxylation of alkyl formates to alkanes with up to 82 % yield.

Source: ChemCatChem

DOI: 10.1002/cctc.70690

Authors: Félix Mandelaire, Thibault Cantat, Lucile Anthore‐Dalion

Institutions: Centre National de la Recherche Scientifique, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, Université Paris-Saclay

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: Agence Nationale de la Recherche, Centre National de la Recherche Scientifique, Commissariat à l'Énergie Atomique et aux Énergies Alternatives, European Research Council

Awards: Transfer Carboaminations of Alkenes with O-Acylated Hydroxylamines, G5988221723, G7341280923