Mizoroki-Heck-type transformations in natural product synthesis: Case studies in carbopalladation and forging all-carbon quaternary stereocenters

The palladium-catalyzed Mizoroki-Heck reaction involves the cross-coupling of organic electrophiles with olefins. This perspective presents a selection of case studies that reveal and exploit interesting fundamental aspects of carbopalladation in Mizoroki-Heck-type processes or associated reaction cascades. Emphasis is placed on examples from total syntheses in which such cross-couplings have facilitated the selective construction of all-carbon quaternary stereocenters to ultimately create access to structurally diverse polycyclic natural products. As part of this, mechanistic considerations of Mizoroki-Heck cross-couplings of non-directed, unbiased tri- and tetra-substituted olefins are also examined and discussed.