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Uncovering the mechanism of the Ag(I)/persulfate-catalyzed cross-coupling reaction of arylboronic acids and heteroarenes.

ABSTRACT: The catalytic cross-coupling of arylboronic acids with pyridines through single-electron oxidation 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 reduction 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.

SUBMITTER: Patel NR

PROVIDER: S-EPMC3665604 | biostudies-literature | 2013 Mar

REPOSITORIES: biostudies-literature

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Uncovering the mechanism of the Ag(I)/persulfate-catalyzed cross-coupling reaction of arylboronic acids and heteroarenes.

Patel Niki R NR Flowers Robert A RA

Journal of the American Chemical Society 20130318 12

The catalytic cross-coupling of arylboronic acids with pyridines through single-electron oxidation 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 a ...[more]

PMID: 23477364

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