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Peer-reviewedCC BY-NC-ND 4.0ChemCatChem

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

  • Félix Mandelaire
  • Thibault Cantat
  • Lucile Anthore-Dalion
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Abstract

The selective cleavage of the C–O bond of unactivated alkyl esters remains a major challenge to use them as C(sp³)‐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⁺, Ca²⁺, Mg²⁺, and Al³⁺) in accelerating C–O bond cleavage. Kinetic analyses demonstrate a seven‐order‐of‐magnitude rate enhancement when replacing LiI with AlI₃. To highlight the synthetic potential of this finding, we further integrate this reactivity into a tandem catalytic system combining AlI₃ and a ruthenium catalyst, achieving efficient protodecarboxylation of alkyl formates to alkanes with up to 82 % yield.

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Cite

BibTeXRIS
BibTeX
@article{mandelaire2026controlled,
  title = {{Controlled Dealkylation of Alkyl Esters With Halide Salts and Application in Tandem‐Catalyzed Protodecarboxylation of Organic Formates}},
  author = {Félix Mandelaire and Thibault Cantat and Lucile Anthore-Dalion},
  journal = {ChemCatChem},
  year = {2026},
  month = oct,
  doi = {10.1002/cctc.70690},
  url = {https://hal.science/hal-05788196v1},
  note = {CC BY-NC-ND 4.0},
}
RIS
TY  - JOUR
TI  - Controlled Dealkylation of Alkyl Esters With Halide Salts and Application in Tandem‐Catalyzed Protodecarboxylation of Organic Formates
AU  - Félix Mandelaire
AU  - Thibault Cantat
AU  - Lucile Anthore-Dalion
PY  - 2026
DA  - 2026/10/09
JO  - ChemCatChem
DO  - 10.1002/cctc.70690
UR  - https://hal.science/hal-05788196v1
AB  - The selective cleavage of the C–O bond of unactivated alkyl esters remains a major challenge to use them as C(sp³)‐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⁺, Ca²⁺, Mg²⁺, and Al³⁺) in accelerating C–O bond cleavage. Kinetic analyses demonstrate a seven‐order‐of‐magnitude rate enhancement when replacing LiI with AlI₃. To highlight the synthetic potential of this finding, we further integrate this reactivity into a tandem catalytic system combining AlI₃ and a ruthenium catalyst, achieving efficient protodecarboxylation of alkyl formates to alkanes with up to 82 % yield.
SN  - 1867-3880
SN  - 1867-3899
ER  -