Abstract
Transannular reactions are unique in that they take advantage of the conformational constraint imposed by the medium‐ or macro‐cyclic substrates to bring reaction centers close to each other. The results are that reactions with a high activation barrier at intermolecular settings are made possible, and more importantly, the often well‐defined conformational bias of cyclic substrates is translated into high regioselectivity and stereoselectivity of the reactions. This tutorial review gives an overview of transannular cyclizations organized by reaction type with an emphasis on applications in natural product synthesis. A section on “memory of chirality,” which focuses on asymmetric transannular transformations with “chiral center‐free” transition states, is also given.
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