Metal-Free Aryl Cross-Coupling Directed by Traceless Linkers
Haensch VG, Neuwirth T, Steinmetzer J, Kloss F, Beckert R, Gräfe S, Kupfer S, Hertweck C (2019)
Publication Type: Journal article
Publication year: 2019
Journal
Book Volume: 25
Pages Range: 16068-16073
Journal Issue: 70
Abstract
The metal-free, highly selective synthesis of biaryls poses a major challenge in organic synthesis. The scope and mechanism of a promising new approach to (hetero)biaryls by the photochemical fusion of aryl substituents tethered to a traceless sulfonamide linker (photosplicing) are reported. Interrogating photosplicing with varying reaction conditions and comparison of diverse synthetic probes (40 examples, including a suite of heterocycles) showed that the reaction has a surprisingly broad scope and involves neither metals nor radicals. Quantum chemical calculations revealed that the C−C bond is formed by an intramolecular photochemical process that involves an excited singlet state and traversal of a five-membered transition state, and thus consistent ipso–ipso coupling results. These results demonstrate that photosplicing is a unique aryl cross-coupling method in the excited state that can be applied to synthesize a broad range of biaryls.
Involved external institutions
Leibniz-Institut für Naturstoff-Forschung und Infektionsbiologie (Hans-Knöll-Institut (HKI)) / Leibniz Institute for Natural Product Research and Infection Biology
Germany (DE)
Friedrich-Schiller-Universität Jena
Germany (DE)
Germany (DE)
Friedrich-Schiller-Universität Jena
Germany (DE)
How to cite
APA:
Haensch, V.G., Neuwirth, T., Steinmetzer, J., Kloss, F., Beckert, R., Gräfe, S.,... Hertweck, C. (2019). Metal-Free Aryl Cross-Coupling Directed by Traceless Linkers. Chemistry - A European Journal, 25(70), 16068-16073. https://doi.org/10.1002/chem.201903582
MLA:
Haensch, Veit G., et al. "Metal-Free Aryl Cross-Coupling Directed by Traceless Linkers." Chemistry - A European Journal 25.70 (2019): 16068-16073.
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