Journal
CHEMISTRY-A EUROPEAN JOURNAL
Volume 25, Issue 70, Pages 16068-16073Publisher
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201903582
Keywords
biaryls; cross-coupling; density functional calculations; photochemistry; synthetic methods
Categories
Funding
- Deutsche Forschungsgemeinschaft
- Federal Ministry of Education and Research (BMBF) of Germany [FKZ 03ZZ0803]
- State of Thuringia [2018 FGI 0039]
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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.
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