We introduce an oxidative Heck reaction for selective complex diene and polyene formation. The reaction proceeds via oxidative Pd(II)/sulfoxide catalysis that retards palladium-hydride isomerizations which previously limited the Heck manifold's capacity for furnishing stereodefined conjugated dienes. Limiting quantities of nonactivated terminal olefins (1 equiv) and slight excesses of vinyl bor...

The synthesis of a previously undescribed sp3-rich 6-5-5-6 tetracyclic ring scaffold using a palladium catalysed domino Heck-Suzuki reaction is reported. This reaction is high-yielding, selective for the domino process over the direct Suzuki reaction and tolerant towards a variety of boronic acids. The novel scaffold can also be accessed via domino Heck-Stille and radical cyclisations. Compound...

During the past decades, building on the seminal contributions of Overman and Shibasaki, the asymmetric intramolecular Heck reaction has been successfully applied in natural product synthesis to install tertiary and quaternary stereocenters. In stark contrast, the intermolecular version of this asymmetric transformation has not reached the same level of development and its synthetic utility rem...