Claisen rearrangement triggered by transition metal-catalyzed alkyne alkoxylation

The highly efficient and selective construction of carbon–carbon bond in an atom-economic and mild way is still one of the cores of modern organic synthesis. The strategy of Claisen rearrangement triggered by catalytic alkyne alkoxylation shows the unique advantage in the carbon–carbon bond formation and has attracted widespread attention during the past two decades. The intramolecular protocol is usually regarded as a powerful tool for the synthesis of functionalized heterocycles, which are widely distributed in natural products and bioactive molecules. Meanwhile, the catalytic intermolecular tandem cyclization/Claisen rearrangement also provides a facile and practical approach for the rapid construction of complicated compounds, which contain valuable core skeletons of various targeted molecules. Recent advances in this rapidly expanding field involving transition metal-catalyzed tandem alkyne alkoxylation/Claisen rearrangement were introduced in this minireview. These related articles were organized via different catalytic species: single-metal catalysis and bimetallic catalysis. A discussion of the reaction scope, mechanistic insights, and synthetic applications of this tandem process is presented.