Abstract Higher‐order cycloadditions present significant potential as a convenient approach for creating higher‐order ring systems, having immense potential in organic and natural product chemistry. The (8 + 2) cycloaddition reaction is a versatile tool in organic chemistry, enabling the efficient synthesis of complex cyclic structures with applications in material science and pharmaceuticals. This review summarizes developments in (8 + 2) cycloaddition since 2008, highlighting the use of tropones, tropothiones, heptafulvenes, and aza‐heptafulvenes with olefins and benzyne as 2π‐components. It emphasizes the need for exploring new 8π‐components with hetero‐dienophile‐based 2π‐components to form diverse higher‐order heterocycles and further investigates intramolecular versions of the (8 + 2) cycloaddition. This article aims to review the recent progress made in the field of (8 + 2) cycloaddition reactions in the realm of organic synthesis since 2008.
Bhargava et al. (Wed,) studied this question.
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