Dearomative Multifunctionalization of Benzene Rings Enabled by Electron-Transfer Catalysis
Abstract
Transforming simple benzene-ring-containing compounds from bulk chemicals into complex three-dimensional molecules with diverse functionalities and controllable stereochemistry under mild, scalable conditions remains a long-standing goal in synthetic chemistry. Dianions generated from aryl carbonyl compounds by two-electron transfer are promising precursors for dearomative difunctionalization. However, previous methods1 for generating dianion intermediates require harsh conditions and are incompatible with functionalized electrophiles, while competing benzylic functionalization via ketyl radical anions2,3 further limits their application. A key challenge is therefore to rapidly convert radical anions into higher-energy dianions using a mild reducing agent, outcompeting nucleophilic reactions of radical anions while ensuring electrophile compatibility. Here we report an ultrafast electron-transfer catalytic mode employing a bipyridine-based catalyst that rapidly acquires electrons from magnesium metal and transfers them to aryl ketyl radical anions, enabling the efficient in situ generation of dianion intermediates from simple aryl ketones under mild conditions. Using chlorosilanes as electrophiles, we obtain dearomatized bis-silylated products bearing conjugated enol silyl ether and allylsilane motifs in up to 98% yield. These products serve as versatile platform molecules for dearomative multifunctionalization, enabling the highly stereoselective synthesis of complex compounds with multiple stereocentres.
Related
- GSH-derived carbon dot-mediated interfacial electron transfer modulates pH-Dependent redox catalysis of Ce-MOF nanozymes for wound healing
- Light-Driven Electron-Transfer Catalysis on Earth-Abundant CuFeS2 Nanocrystals Probed by Operando SERS
- Triple energy transfer-enabled dearomative cycloaddition/rearrangement cascade of bicyclic azaarenes to structurally complex products
- Vibrational Activation Triggers Ultrafast Excited State Intramolecular Proton Transfer in Single-Benzene Fluorophores
- Tuning the Efficiency of Iridium(III) Complexes for Energy Transfer (EnT) Catalysis through Ligand Design
BibTeX
@misc{li2026dearomative,
title = {{Dearomative Multifunctionalization of Benzene Rings Enabled by Electron-Transfer Catalysis}},
author = {Meng Li and Nan-Nan Li and Cai-Lan Kou and Zi-Yi Chen and Xi Luo and Jian-Bo Xie},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008908/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008908/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Dearomative Multifunctionalization of Benzene Rings Enabled by Electron-Transfer Catalysis
AU - Meng Li
AU - Nan-Nan Li
AU - Cai-Lan Kou
AU - Zi-Yi Chen
AU - Xi Luo
AU - Jian-Bo Xie
PY - 2026
DA - 2026/09/16
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008908/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008908/v1
AB - Transforming simple benzene-ring-containing compounds from bulk chemicals into complex three-dimensional molecules with diverse functionalities and controllable stereochemistry under mild, scalable conditions remains a long-standing goal in synthetic chemistry. Dianions generated from aryl carbonyl compounds by two-electron transfer are promising precursors for dearomative difunctionalization. However, previous methods1 for generating dianion intermediates require harsh conditions and are incompatible with functionalized electrophiles, while competing benzylic functionalization via ketyl radical anions2,3 further limits their application. A key challenge is therefore to rapidly convert radical anions into higher-energy dianions using a mild reducing agent, outcompeting nucleophilic reactions of radical anions while ensuring electrophile compatibility. Here we report an ultrafast electron-transfer catalytic mode employing a bipyridine-based catalyst that rapidly acquires electrons from magnesium metal and transfers them to aryl ketyl radical anions, enabling the efficient in situ generation of dianion intermediates from simple aryl ketones under mild conditions. Using chlorosilanes as electrophiles, we obtain dearomatized bis-silylated products bearing conjugated enol silyl ether and allylsilane motifs in up to 98% yield. These products serve as versatile platform molecules for dearomative multifunctionalization, enabling the highly stereoselective synthesis of complex compounds with multiple stereocentres.
ER -