Dyotropic Rearrangements in Organic Synthesis
Summary
Dyotropic rearrangements constitute a class of concerted pericyclic processes in which two σ-bonds migrate simultaneously around a cyclic or acyclic framework. First recognised in the mid-20th century, these transformations have been classified into Type I, involving intramolecular interchange of two vicinal substituents across a single bond, and Type II, where non-vicinal groups exchange positions through a bicyclic transition state. Mechanistic insights, derived from both kinetics and computational chemistry, reveal that the synchronicity of bond migrations and the relative migration aptitude of substituents govern stereochemical outcomes. Over the past decade, the utility of dyotropic rearrangements has expanded into the synthesis of complex scaffolds, enabling streamlined access to polycyclic natural products, advanced intermediates for medicinal chemistry and spirocyclic motifs. Catalytic variants leveraging chiral Lewis acids or organocatalysts have begun to introduce enantioselectivity, while gas-phase and solid-state implementations demonstrate the versatility of this rearrangement in both academic and industrial settings.
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Dyotropic Rearrangements in Organic Synthesis publication trend
The graph below shows the total number of articles in dyotropic rearrangements in organic synthesis across all publications each year (not limited to Nature Index journals).
Technical terms
Dyotropic rearrangement: A concerted pericyclic process in which two σ-bonds migrate simultaneously to new positions within a molecule.
Migration aptitude: A relative measure of how readily different substituents undergo bond migration in pericyclic rearrangements.
Pericyclic reaction: A thermally or photochemically induced reaction proceeding through a cyclic array of bonding changes in a single step without intermediates.
Asynchronicity: The degree to which bond-breaking and bond-forming events occur at different rates during a concerted pericyclic transition state.
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