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.

A gem‐Dibromocyclopropane Ring‐Expansion/Mizoroki‐Heck Cyclisation Route to Tetrahydrodibenzofurans

“…Our ongoing interest in the preparation of biologically active congeners of compounds 1-3 prompted the study detailed herein with the approach taken (Figure 2) being based on the premise that the pivotal C9a-C9b bond of the signature framework 4 could be established, together with the central Bring, by subjecting precursor 5 to an intramolecular Mizoroki-Heck arylation reaction. [5] In this scenario, the A-ring double bond in product 4 would be uniquely positioned and poised for functionalization in ways that would afford other distinctively substituted tetrahydrodibenzofurans and related systems. Compound 5 was, in turn, expected to be readily obtained through nucleophilic trapping of the π-allylcation 6 by phenol (7) and with the electrophile (6) being generated through electrocyclic ring-opening of the ring-fused gem-dibromocyclopropane 8, [6] a framework that is itself readily formed through dibromocarbene addition to cyclopentene (9).…”

Palladium-Catalyzed Three-Component Cascade Carbonylation Reaction to Construct Benzofuran Derivatives

“…So far, most methods of introducing carbonyl groups are mainly based on in situ carbonylatio catalyzed by the transition metal palladium orrhodium. With the rapid development of transition metal-catalyzed domino reactions, research on the construction of complex skeletons through intermolecular or intramolecular tandem cyclization strategies has become increasingly prominent . In particular, the palladium-catalyzed domino carbonylation reaction is favored by many scientific researchers (Scheme c).…”