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The Diels–Alder reaction stands as one of the most pivotal transformations in organic chemistry. Its efficiency, marked by the formation of two carbon‐carbon bonds and up to four new stereocenters in a single step, underscores its versatility and indispensability in synthesizing natural products and pharmaceuticals. The most significant stereoselectivity feature is the “endo rule”. While this rule...
Delving into recent examples of exo‐Diels–Alder reactions, this review sheds light on the factors that invert the intrinsic tendency. The aim is to provide a comprehensive understanding of how to predict and design exo‐Diels–Alder reactions, paving the way for new diastereoselective catalyst systems and expanding the chemical scope of Diels–Alder reactions. More information can be found in the Review...