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O-, N- and C-bicyclopentylation using thianthrenium reagents

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Alvarez,  Eva Maria
Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institute of Organic Chemistry, RWTH Aachen University;

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Bai,  Zibo
Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Pandit,  Saikat
Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society;
Institute of Organic Chemistry, RWTH Aachen University;

Frank,  Nils
Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Torkowski,  Luca
Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Ritter,  Tobias
Research Department Ritter, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Citation

Alvarez, E. M., Bai, Z., Pandit, S., Frank, N., Torkowski, L., & Ritter, T. (2023). O-, N- and C-bicyclopentylation using thianthrenium reagents. Nature Synthesis, 2, 548-556. doi:10.1038/s44160-023-00277-8.


Cite as: https://hdl.handle.net/21.11116/0000-000D-2D97-7
Abstract
Rigid 1,3-disubstituted bicyclo[1.1.1]pentanes (BCPs) are linear bioisosteres for para-substituted benzene rings in drug development and can lead to an improved pharmacokinetic profile. The construction of BCPs commonly requires the cumbersome use of labile [1.1.1]propellane in solution, and more stable reagents do not show the versatile reactivity of propellane itself. Here we report stable thianthrenium-based BCP reagents for practical O-, N- and C-alkylation reactions that expand the scope of bicyclopentylation beyond that of any other reagent, including [1.1.1]propellane. The redox and stereoelectronic properties of the thianthrene scaffold are relevant for both the synthesis of the BCP-thianthrenium reagents via strain release as well as their subsequent reactivity. The weak exocyclic C–S bond can undergo selective mesolytic cleavage upon single-electron reduction to produce BCP radicals that engage in transition metal-mediated C–O, C–N and C–C bond formations, even at a late stage of multistep reactions with a wide variety of functional groups present.