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Regioselective Thiolation and Selenylation of Cyclic Diaryl λ3-Bromanes Enabled by Visible-Light Photocatalysis
Xue-Ying Yang1, Qiang Wang2, Si-Rui Jia1
1Hubei Key Laboratory for Precision Synthesis of Small Molecule Pharmaceuticals and Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062, P. R. China.
Abstract:
Despite the broad utility of cyclic diaryl λ3-bromanes as aryne precursors for nucleophilic additions by heteroatom-based nucleophiles under mild basic conditions, their capacity to install arylchalcogen bonds in a regioselective manner is largely unexplored and challenging. The higher oxidative addition barrier of cyclic diaryl λ3-bromanes relative to their iodine analogues leads to transition-metal-catalyzed aryl-chalcogen bond formation requiring more forcing conditions, which decreases the regioselectivity. Moreover, the oxidizing character of hypervalent bromanes might be problematic. Herein, we disclose a photocatalytic strategy to achieve highly regioselective thiolation and selenylation of cyclic diaryl λ3-bromanes. This reaction proceeds under mild reaction conditions and exhibits a broad substrate scope with a good functional group tolerance and excellent regioselectivity.
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