Learning Chemoselectivity in a Low-Data Regime: Bayesian Optimization of the NBS-Activated Selenocyclization of α-Allenols
4 affiliations
- 1Department of Chemistry, University of Helsinki, A. I. Virtasen aukio 1, Helsinki, Finland, 00560
- 2IMC Krems University of Applied Sciences
- 3Department of Materials Science & Environmental Engineering
- 4Tampere University
Abstract
The activation of diaryl diselenides with N-bromosuccinimide generates two competing electrophiles, and with α-allenols as the π-nucleophiles, product mixtures of brominated and selenylated dihydrofurans can arise. This selectivity challenge was quickly resolved through a Bayesian optimization campaign over seven reaction parameters covering >2000 discrete combinations. Fifteen randomly sampled experiments were sufficient for Gaussian-process surrogate models that, when asked to simultaneously maximize yield and selectivity, recommended conditions that delivered the 3-selanyl-2,5-dihydrofuran in up to 74% yield with complete suppression of the vinyl bromide. The identified protocol for the 5-endo-trig cyclization transferred without re-optimization to a range of structurally diverse α-allenols (50–81% isolated yield) and proved to be applicable to other dichalcogenides, as well as to the 6-endo-trig cyclization of related allene homologues.
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BibTeX
@misc{gocht2026learning,
title = {{Learning Chemoselectivity in a Low-Data Regime: Bayesian Optimization of the NBS-Activated Selenocyclization of α-Allenols}},
author = {Benedikt Gocht and Andrei Costea and Anna Tyshchenko and Janne M. Naapuri and Jan Deska},
howpublished = {ChemRxiv},
year = {2026},
month = oct,
doi = {10.26434/chemrxiv.15011183/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011183/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Learning Chemoselectivity in a Low-Data Regime: Bayesian Optimization of the NBS-Activated Selenocyclization of α-Allenols
AU - Benedikt Gocht
AU - Andrei Costea
AU - Anna Tyshchenko
AU - Janne M. Naapuri
AU - Jan Deska
PY - 2026
DA - 2026/10/28
PB - ChemRxiv
DO - 10.26434/chemrxiv.15011183/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15011183/v1
AB - The activation of diaryl diselenides with N-bromosuccinimide generates two competing electrophiles, and with α-allenols as the π-nucleophiles, product mixtures of brominated and selenylated dihydrofurans can arise. This selectivity challenge was quickly resolved through a Bayesian optimization campaign over seven reaction parameters covering >2000 discrete combinations. Fifteen randomly sampled experiments were sufficient for Gaussian-process surrogate models that, when asked to simultaneously maximize yield and selectivity, recommended conditions that delivered the 3-selanyl-2,5-dihydrofuran in up to 74% yield with complete suppression of the vinyl bromide. The identified protocol for the 5-endo-trig cyclization transferred without re-optimization to a range of structurally diverse α-allenols (50–81% isolated yield) and proved to be applicable to other dichalcogenides, as well as to the 6-endo-trig cyclization of related allene homologues.
ER -