The synthesis of biaryls and vinylarenes by Pd(II)-catalyzed oxidative coupling of two C(sp<sup>2</sup>)−H bonds represents an attractive, direct route to these prevalent motifs. We recently reported a method for heteroarene C−H alkenylation using simple thioether ligands that enable significant rate acceleration and switchable site selectivity. A new thioether-enabled method for heteroarene homocoupling will be discussed that can construct privileged optoelectronic scaffolds in a streamlined fashion without the typical need for (super)stoichiometric silver or copper reagents. A combined experimental and computational mechanistic study will also be discussed that correlates the thioether catalytic effects to an electrophilic concerted metalation-deprotonation (<i>e</i>CMD) mechanism of C−H cleavage, which is distinct from the step-wise electrophilic metalation (EM) pathway generally invoked in dehydrogenative coupling reactions of electron-rich (hetero)arenes.

Thioether-palladium catalysis for efficient oxidative heteroarene C−H functionalization

255th National Meeting (2018)

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