Carboxyl–Group Removal and Return: Mechanistic and Strategic Advances in Decarboxylation–Carboxylation
4 affiliations
- 1Department of Chemistry, KU Leuven, Celestijnenlaan 200F, Leuven, Belgium, B-3001
- 2College of Chemistry and Chemical Engineering
- 3Shanghai University of Engineering Science
- 4Peoples’ Friendship University of Russia (RUDN University, Miklukho-Maklaya Street 6, Moscow, Russia, 117198
Abstract
Carboxylic acids are ubiquitous functionalities and indispensable synthetic linchpins in organic chemistry. In recent years, strategies involving the removal, exchange, or recycling of the carboxyl group, particularly decarboxylation and carboxylation have gained remarkable momentum, partly driven by the imperative to valorize carbon dioxide generated in chemical transformations. Beyond simple CO2 extrusion, tandem decarboxylation–carboxylation and related cyclic processes have emerged as powerful yet underexplored approaches for constructing carboxylic acids in a single operation. This review highlights recent advances (2000–2026) in decarboxylation–re-carboxylation chemistry, with an emphasis on mechanistic understanding, reactive intermediates, and the strategic use of CO2 as a transient functional handle. We introduce a unified conceptual framework that classifies carboxyl–group transfer based on the identity of the carbon shuttle, the timing and mode of carboxyl reintroduction, and the nature of reactive intermediates. Subsequent sections discuss three major mechanistic archetypes: CO2–cycling decarboxylation–re-carboxylation, ester–cycling decarboxylation–re-esterification, and non-in situ carboxyl transfer using exogenous CO2 or alternative carboxyl sources. By delineating key developments and conceptual trends, we aim to inspire further innovation in exploiting carboxyl–group recycling as a platform for sustainable molecular synthesis.
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BibTeX
@misc{xie2026carboxylgroup,
title = {{Carboxyl–Group Removal and Return: Mechanistic and Strategic Advances in Decarboxylation–Carboxylation}},
author = {Yujuan Xie and Liliang Huang and Huangdi Feng and Erik V. Van der Eycken},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009877/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009877/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Carboxyl–Group Removal and Return: Mechanistic and Strategic Advances in Decarboxylation–Carboxylation
AU - Yujuan Xie
AU - Liliang Huang
AU - Huangdi Feng
AU - Erik V. Van der Eycken
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009877/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009877/v1
AB - Carboxylic acids are ubiquitous functionalities and indispensable synthetic linchpins in organic chemistry. In recent years, strategies involving the removal, exchange, or recycling of the carboxyl group, particularly decarboxylation and carboxylation have gained remarkable momentum, partly driven by the imperative to valorize carbon dioxide generated in chemical transformations. Beyond simple CO2 extrusion, tandem decarboxylation–carboxylation and related cyclic processes have emerged as powerful yet underexplored approaches for constructing carboxylic acids in a single operation. This review highlights recent advances (2000–2026) in decarboxylation–re-carboxylation chemistry, with an emphasis on mechanistic understanding, reactive intermediates, and the strategic use of CO2 as a transient functional handle. We introduce a unified conceptual framework that classifies carboxyl–group transfer based on the identity of the carbon shuttle, the timing and mode of carboxyl reintroduction, and the nature of reactive intermediates. Subsequent sections discuss three major mechanistic archetypes: CO2–cycling decarboxylation–re-carboxylation, ester–cycling decarboxylation–re-esterification, and non-in situ carboxyl transfer using exogenous CO2 or alternative carboxyl sources. By delineating key developments and conceptual trends, we aim to inspire further innovation in exploiting carboxyl–group recycling as a platform for sustainable molecular synthesis.
ER -