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Photochemical Carbene Transfer Reactions of Aryl/Aryl Diazoalkanes – Experiment and Theory

preprint
submitted on 29.10.2020, 09:16 and posted on 30.10.2020, 08:57 by Sripati Jana, Chao Pei, Claire Empel, Rene Koenigs
The photochemical carbene transfer reaction is a timely strategy in organic synthesis and generally proceeds via singlet carbene intermediates. In this combined experimental and computational studies, we show that the photolysis reaction of diaryl diazoalkanes gives access to both singlet and triplet diarylcarbene intermediates. The electronic properties of substituents of the aryl substituents show a strong influence on the electronic properties of the carbene intermediate and result in significantly reduced singlet triplet energy gaps. Depending on the spin state and electronic properties of the carbene intermediate, the reaction with alkynes provides access towards chemoselective cyclopropenation, cascade, or C-H functionalization reactions.

Funding

Deutsche Forschungsgemeinschaft

History

Email Address of Submitting Author

rene.koenigs@rwth-aachen.de

Institution

RWTH Aachen University

Country

Germany

ORCID For Submitting Author

0000-0003-0247-4384

Declaration of Conflict of Interest

The authors declare no conflict of interest.

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