Rhenium-catalysed reactions in chemical synthesis: selected case studies.

This Perspective presents and discusses a selection of examples that reinforce the enabling and distinctive reactivity provided by homogeneous rhenium catalysis in chemical synthesis. Specifically, the ability for lower oxidation state rhenium-carbonyl catalysts to engage alkyne, allene, and enol substrates in various carbon-carbon bond-forming reactions is highlighted. The inherent capacity of Lewis acidic, higher oxidation state oxorhenium catalysts to facilitate the transposition/isomerisation of allyl alcohols and attendant functionalisation via reaction cascades is also showcased. A brief overview of representative rhenium catalysts that have allowed for reductions of imines, carbonyls, and related compounds is also provided.