Autocatalytic Deprotection of Diboronate‐Protected Quinones via Redox Cross‐Catalysis: Mechanistic Insights Into Double Masking Strategies
Abstract
We report an autocatalytic molecular amplification system based on the double masking of benzoquinones with boronate ester protecting groups (i.e., diboronate ester probes). This design extends a previously described redox cross‐catalytic (RCC) reaction scheme, in which hydrogen peroxide (H2O2 ) and quinones are exponentially co‐generated through coupled catalytic loops. The double protection aims to enhance the chemical stability of the diboronate probes while preserving their ability to undergo autocatalytic deprotection. Through kinetic modeling and experimental validation, we demonstrate that complete deprotection to the corresponding quinones can occur even under substoichiometric H2O2 conditions, thereby sustaining autocatalytic behavior. Comparative studies of symmetric and asymmetric diboronate probes reveal how molecular structure and electronic effects control the kinetics of each deprotection step and so the overall amplification efficiency. Finally, we show that these doubly protected systems enable efficient responses to H2O2 across more than two orders of magnitude in concentration (from µM to sub‐millimolar range) and within minutes, while providing improved probe stability and tunable reactivity. This work offers mechanistic insights and design principles for next‐generation autocatalytic redox amplification systems with enhanced analytical performance.
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BibTeX
@article{hui2026autocatalytic,
title = {{Autocatalytic Deprotection of Diboronate‐Protected Quinones via Redox Cross‐Catalysis: Mechanistic Insights Into Double Masking Strategies}},
author = {Pan Hui and Alexandra Pastor and Mathieu Branca and Benoît Limoges and François Mavré},
journal = {ChemSystemsChem},
year = {2026},
month = may,
doi = {10.1002/syst.70042},
url = {https://hal.science/hal-05760559v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Autocatalytic Deprotection of Diboronate‐Protected Quinones via Redox Cross‐Catalysis: Mechanistic Insights Into Double Masking Strategies
AU - Pan Hui
AU - Alexandra Pastor
AU - Mathieu Branca
AU - Benoît Limoges
AU - François Mavré
PY - 2026
DA - 2026/05/29
JO - ChemSystemsChem
DO - 10.1002/syst.70042
UR - https://hal.science/hal-05760559v1
AB - We report an autocatalytic molecular amplification system based on the double masking of benzoquinones with boronate ester protecting groups (i.e., diboronate ester probes). This design extends a previously described redox cross‐catalytic (RCC) reaction scheme, in which hydrogen peroxide (H2O2 ) and quinones are exponentially co‐generated through coupled catalytic loops. The double protection aims to enhance the chemical stability of the diboronate probes while preserving their ability to undergo autocatalytic deprotection. Through kinetic modeling and experimental validation, we demonstrate that complete deprotection to the corresponding quinones can occur even under substoichiometric H2O2 conditions, thereby sustaining autocatalytic behavior. Comparative studies of symmetric and asymmetric diboronate probes reveal how molecular structure and electronic effects control the kinetics of each deprotection step and so the overall amplification efficiency. Finally, we show that these doubly protected systems enable efficient responses to H2O2 across more than two orders of magnitude in concentration (from µM to sub‐millimolar range) and within minutes, while providing improved probe stability and tunable reactivity. This work offers mechanistic insights and design principles for next‐generation autocatalytic redox amplification systems with enhanced analytical performance.
SN - 2570-4206
ER -