Organocatalytic asymmetric synthesis of Si-stereogenic silacycles

Han, Jung Tae; Tsuji, Nobuya; Zhou, Hui; Leutzsch, Markus; List, Benjamin

doi:10.1038/s41467-024-49988-2

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Organocatalytic asymmetric synthesis of Si-stereogenic silacycles

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Han, Jung Tae
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Korea Institute of Science and Technology (KIST);

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Zhou, Hui
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Leutzsch, Markus
Service Department Farès (NMR), Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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List, Benjamin
Research Department List, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University;

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Citation

Han, J. T., Tsuji, N., Zhou, H., Leutzsch, M., & List, B. (2024). Organocatalytic asymmetric synthesis of Si-stereogenic silacycles. Nature Communications, 15: 5846. doi:10.1038/s41467-024-49988-2.

Cite as: https://hdl.handle.net/21.11116/0000-000F-9FBE-9

Abstract

A strong and confined Brønsted acid catalyzed enantioselective cyclization of bis(methallyl)silanes provides enantioenriched Si-stereogenic silacycles. High enantioselectivities of up to 96.5:3.5 er were obtained for a range of bis(methallyl)silanes. NMR and ESI-MS studies reveal that the formation of a covalent adduct irreversibly inhibits turnover. Remarkably, we found that acetic acid as an additive promotes the collapse of this adduct, enabling full turnover. Experimental investigation and density functional theory (DFT) calculations were conducted to elucidate the origin of this phenomenon and the observed enantioselectivity.