Transition‐Metal‐Catalyzed Transformations Involving the Heck Reaction

Abstract Elaborated molecular architectures including complex carbocycles, heterocycles, and polycyclic molecular structures represent an important class of organic compounds because they are ubiquitous structural units in a broad variety of biologically and pharmacologically relevant natural products, medicinal molecules, and functional materials. A major challenge in modern synthetic methodology is the development of strategically efficient and selective construction of these compounds from readily available starting materials. Transition‐metal‐catalyzed transformations involving Heck reaction as the pivotal step have afforded a powerful approach for accessing sophisticated polycyclic skeletons from a set of easy‐to handle starting materials, thus highlighting its potential significance in streamlining the drug discovery process. Over the past few decades, significant effort has been devoted to accessing complex polycyclic derivatives in efficient and versatile routes, and a number of powerful and direct synthetic strategies have been reported. In this review, the latest advances in transition‐metal‐catalyzed transformations involving Heck reaction as the critical step are summarized, which could be divided into six categories: 1) Heck/Sonogashira tandem reaction; 2) Heck/Suzuki tandem reaction; 3) Heck/Heck tandem reaction; 4) Heck/Hiyama tandem reaction; 5) Heck/Cacchi tandem reaction; 6) Heck/C−H bond functionalization tandem reaction.