Uncovering the Mechanism of the Ag(I)​/Persulfate-​Catalyzed Cross-​Coupling Reaction of Arylboronic Acids and Heteroarenes

TitleUncovering the Mechanism of the Ag(I)​/Persulfate-​Catalyzed Cross-​Coupling Reaction of Arylboronic Acids and Heteroarenes
Publication TypeJournal Article
Year of Publication2013
AuthorsPatel NR
Secondary AuthorsFlowers RA
JournalJournal of the American Chemical Society
Volume135
Issue12
Start Page4672
Pagination4675
Date Published03/2013
Abstract

The catalytic cross-​coupling of arylboronic acids with pyridines through single-​electron oxidn. provides efficient access to substituted heterocycles. Despite the importance of this reaction, very little is known about its mechanism, and as a consequence, it is unclear whether the full scope of the transformation has been realized. Here we present kinetic and spectroscopic evidence showing a high degree of complexity in the reaction system. The mechanism derived from these studies shows the activation of Ag(I) for redn. of persulfate and an off-​cycle protodeboronation by the pyridine substrate. These results provide key mechanistic insights that enable control of the off-​cycle process, thus providing higher efficiency and yield.