Shlapakov, Nikita S. and Kobelev, Andrey D. and Burykina, Julia V. and Kostyukovich, Alexander Yu. and Koenig, Burkhard and Ananikov, Valentine P. (2024) Reversible Radical Addition Guides Selective Photocatalytic Intermolecular Thiol-Yne-Ene Molecular Assembly. ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 63 (13). ISSN 1521-3773
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In modern organic chemistry, harnessing the power of multicomponent radical reactions presents both significant challenges and extraordinary potential. This article delves into this scientific frontier by addressing the critical issue of controlling selectivity in such complex processes. We introduce a novel approach that revolves around the reversible addition of thiyl radicals to multiple bonds, reshaping the landscape of multicomponent radical reactions. The key to selectivity lies in the intricate interplay between reversibility and the energy landscapes governing C-C bond formation in thiol-yne-ene reactions. The developed approach not only allows to prioritize the thiol-yne-ene cascade, dominating over alternative reactions, but also extends the scope of coupling products obtained from alkenes and alkynes of various structures and electron density distributions, regardless of their relative polarity difference, opening doors to more versatile synthetic possibilities. In the present study, we provide a powerful tool for atom-economical C-S and C-C bond formation, paving the way for the efficient synthesis of complex molecules. Carrying out our experimental and computational studies, we elucidated the fundamental mechanisms underlying radical cascades, a knowledge that can be broadly applied in the field of organic chemistry. A metal-free photoredox three-component coupling of thiols with readily available alkynes and alkenes has been developed. The reaction mechanism was evaluated by combining ESI-HRMS, EPR spectroscopy, isotope labeling and control experiments. The applicability of the reversible radical addition approach for intermolecular reactions and the key role of pi-pi stacking interactions in stereoselectivity control have been shown by DFT studies.+ image
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | STEREODIVERGENT SYNTHESIS; NICKEL; ALKYNES; PHOTOREDOX; CATALYSIS; FUNCTIONALIZATION; CYCLIZATION; OLEFINS; visible light; three-component reaction; photoredox catalysis; reaction mechanisms; atom economy |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Organische Chemie > Lehrstuhl Prof. Dr. Burkhard König |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 16 Dec 2025 08:19 |
| Last Modified: | 16 Dec 2025 08:19 |
| URI: | https://pred.uni-regensburg.de/id/eprint/64379 |
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