Polycyclic Compounds from Allenes via Palladium-Mediated Intramolecular Carbopalladation/Nucleophilic Substitution Cascade Processes

In recent decades transition metals have made a substantial contribution to the development of novel synthetic processes, with palladium catalysis being, arguably, at the forefront of this research. The efficiency of Pd-promoted C–C or C–X bond formation along with a variety of other transformations renders this metal an indispensable tool in synthetic organic chemistry. Of particular interest are Pd-catalysed multicomponent cascade reactions as they often allow the creation of complex structures from relatively simple starting materials, mimicking in this sense biochemical processes. Allenes as partners in Pd-promoted cascades involving carbopalladation/nucleophilic substitutions have been extensively studied in recent years. Many tactical variants have been explored showing a high level of efficiency and chemoselectivity with predictable outcomes. This short review is focused on intramolecular processes of this type because they provide access to relatively complex polycyclic products, possessing structural features often found in natural products and related compounds. Various approaches are discussed with the intention to demonstrate their applicability and synthetic potential. 1 Introduction 2 Intramolecular Palladium-Promoted Cascades of Allenes 3 Class I Cyclisations 4 Class II Cyclisations 5 Class III Cyclisations 6 Class IV Cyclisations 7 Conclusion