Cross-dehydrogenative coupling (CDC) reactions directly form carbon-carbon or carbon-heteroatom bonds from simple hydrocarbon feed stocks and are thus potentially more sustainable methods than traditional cross-coupling reactions that require functionalized substrates. General improvements in catalytic rates and control over selectivity for a particular C–H bond are needed, however, for CDC chemistry to reach full potential and challenge the prominence of cross-coupling. Our efforts to explore and leverage new ligand space to these ends will be discussed in the context of the dehydrogenative Heck reaction (DHR), one of the most common CDC reactions. The mechanistic origins of substantial rate accelerations and cases of unusual selectivity favoring a more hindered site using thioether-coordinated Pd catalysts will be emphasized in the presentation. These observed ligand effects on rate- and selectivity-determining C–H bond cleavage should not be exclusive to the DHR because this key Pd-catalyzed step is generally conserved across numerous CDC reactions.

Mechanism, rate, and selectivity consequences of sulfur ligands in cross-dehydrogenative coupling

254th National Meeting (2017)

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