Hypoboric Acid Catecholate (HAC) Catalysis for Stereoselective Decarboxylative Borylation of Redox-Active Esters
- 1Department of Chemistry
- 2Stockholm University
- 3Institute of Molecular Science (ICMol, University of Valencia, Calle Catedrático José Beltrán, 2, Paterna, Spain, 46980
Abstract
The Hypoboric Acid Catecholate (HAC) is a new class of diboron reagent bearing a borylcatecholato and a boronic acid moiety. Herein, we demonstrate that HACs can also be expontaneously formed in situ from collections of catechols and hypoboric acid. These HACs catalyze the decarboxylative borylation of redox-active esters, providing superior reactivity and selectivity. Equilibrium and kinetic NMR experiments indicate that the catalytic turnover is enabled by the high affinity of catechols for hypoboric acid and their low affinity for boronic acids that is uncovered herein. The catalytic system operates in mild conditions and is robust towards air and moisture, demonstrating its utility in the synthesis of important medicinally-relevant boronates. The enhanced selectivity is sourced in the regioselective radical capture by HAC intermediates at their customized borylcatecholato moiety, which can easily be stereoelectronically tailored for specific applications. These features of the catalytic approach with unsymmetrical HACs presented herein contrast with current state-of-the-art methods based on stoichiometric symmetrical diboron reagents.
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BibTeX
@misc{kohlhepp2026hypoboric,
title = {{Hypoboric Acid Catecholate (HAC) Catalysis for Stereoselective Decarboxylative Borylation of Redox-Active Esters}},
author = {S. V. Kohlhepp and M. Costantini and B. Meana-Baamonde and Abraham Mendoza},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15009869/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009869/v1},
note = {CC BY-NC-ND},
}
RIS
TY - UNPB
TI - Hypoboric Acid Catecholate (HAC) Catalysis for Stereoselective Decarboxylative Borylation of Redox-Active Esters
AU - S. V. Kohlhepp
AU - M. Costantini
AU - B. Meana-Baamonde
AU - Abraham Mendoza
PY - 2026
DA - 2026/10/05
PB - ChemRxiv
DO - 10.26434/chemrxiv.15009869/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15009869/v1
AB - The Hypoboric Acid Catecholate (HAC) is a new class of diboron reagent bearing a borylcatecholato and a boronic acid moiety. Herein, we demonstrate that HACs can also be expontaneously formed in situ from collections of catechols and hypoboric acid. These HACs catalyze the decarboxylative borylation of redox-active esters, providing superior reactivity and selectivity. Equilibrium and kinetic NMR experiments indicate that the catalytic turnover is enabled by the high affinity of catechols for hypoboric acid and their low affinity for boronic acids that is uncovered herein. The catalytic system operates in mild conditions and is robust towards air and moisture, demonstrating its utility in the synthesis of important medicinally-relevant boronates. The enhanced selectivity is sourced in the regioselective radical capture by HAC intermediates at their customized borylcatecholato moiety, which can easily be stereoelectronically tailored for specific applications. These features of the catalytic approach with unsymmetrical HACs presented herein contrast with current state-of-the-art methods based on stoichiometric symmetrical diboron reagents.
ER -