The Diels-Alder reaction has long established its high rank in the toolbox of any natural product chemist. The tremendous toleration of building blocks of various complexity and derivatization degree, as well as the enablement of furnishing six-membered rings with well-defined stereochemistry represents its main features and advantages. In recent years, many total syntheses of natural products relied at some point on the use of a [4+2]-cycloaddition step. Among classic approaches, several modifications of the Diels-Alder reaction, such as hetero-Diels-Alder reactions, dehydro-Diels-Alder reactions or domino-Diels-Alder reactions have been employed to extend the scope in the synthesis of natural products. Our review covers the application of the Diels-Alder reaction in natural product syntheses from 2017 to 2020, as well as selected methodologies which were inspired by, or could be used to access natural products.
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