Cationic Selenuranes Enable Direct Linchpin Formation in Arenes
- 1Institute of Organic Chemistry
- 2University of Vienna
Abstract
The formation of linchpins is a powerful strategy for increasing molecular complexity. Chalcogenonium salts have become valuable intermediates for molecular diversification, owing to their exceptional chemoselectivity in arene C–H functionalization and a synthetic versatility comparable to that of halides and pseudohalides. Sulfonium group introduction through an isohypsic process from S(IV) precursors requires activation with strong acids or anhydrides. Here, we report the direct synthesis of selenonium salts from bench-stable Se(III) cationic selenuranes using a simple dump-and-stir protocol. The transformation proceeds under air at ambient temperature and requires no exogenous activators. Mechanistic investigations reveal high sensitivity to electronic effects (ρ = −10), whereas site selectivity is determined by the rate-limiting deprotonation step (kH/kD = 2.3). The method is scalable to 10.0 mmol (>6.2 g) and provides direct access to selenonium salts derived from complex molecules. The resulting selenonium salts serve as versatile linchpins for photochemical, nucleophilic, and transition-metal-catalyzed transformations, enabling late-stage molecular diversification.
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BibTeX
@misc{zhiliaev2026cationic,
title = {{Cationic Selenuranes Enable Direct Linchpin Formation in Arenes}},
author = {Kirill Zhiliaev and Till Schreyer and Mihai V. Popescu and Javier Mateos},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008541/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008541/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Cationic Selenuranes Enable Direct Linchpin Formation in Arenes
AU - Kirill Zhiliaev
AU - Till Schreyer
AU - Mihai V. Popescu
AU - Javier Mateos
PY - 2026
DA - 2026/09/09
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008541/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008541/v1
AB - The formation of linchpins is a powerful strategy for increasing molecular complexity. Chalcogenonium salts have become valuable intermediates for molecular diversification, owing to their exceptional chemoselectivity in arene C–H functionalization and a synthetic versatility comparable to that of halides and pseudohalides. Sulfonium group introduction through an isohypsic process from S(IV) precursors requires activation with strong acids or anhydrides. Here, we report the direct synthesis of selenonium salts from bench-stable Se(III) cationic selenuranes using a simple dump-and-stir protocol. The transformation proceeds under air at ambient temperature and requires no exogenous activators. Mechanistic investigations reveal high sensitivity to electronic effects (ρ = −10), whereas site selectivity is determined by the rate-limiting deprotonation step (kH/kD = 2.3). The method is scalable to 10.0 mmol (>6.2 g) and provides direct access to selenonium salts derived from complex molecules. The resulting selenonium salts serve as versatile linchpins for photochemical, nucleophilic, and transition-metal-catalyzed transformations, enabling late-stage molecular diversification.
ER -