Hybrid catalysis features the synergistic interplay of two chemical concepts. Recently, the union of radical and organometallic chemistry has become a mainstream approach to solving outstanding challenges in synthetic chemistry. This seminar will highlight the implementation of hybrid catalysis for the development of the first endo-selective Mizoroki–Heck reaction empowered by a single Pd-catalytic cycle featuring hybrid Pd-radical intermediates. Also, the discovery of a mild, efficient, and general protocol for the site-selective desaturation and remote functionalization of ubiquitous aliphatic alcohols via hydrogen-atom-transfer (HAT) of photoinduced hybrid Pd-radical intermediates will be discussed.
Another area of hybrid catalysis features the merger of two catalytic cycles of different inherent natures, such as Transition-Metal (TM)-Photoredox catalysis. This dual approach has resulted in novel C–C bond formation of versatile feedstocks that are otherwise difficult to achieve by traditional means. However, most approaches to date feature the coupling of nucleophiles and electrophiles. Thus, the development of a photoredox assisted cross-electrophile coupling reaction (PACR) could enable novel C–C bond formation and uncover new reactivity. This seminar will feature recent work on the development of a tri-catalytic cross-electrophile coupling of abundant epoxides and (hetero)aryl iodides under visible light. Notably, under otherwise similar conditions, the opposite regiochemical outcomes were observed for the cases of styrenyl and aliphatic terminal epoxides. Mechanistic studies are presented to explain these observations.