Abstract: Molecular rearrangements occupy an important place in organic chemistry because they make it possible to significantly modify organic molecules in a single step to obtain new compounds with desirable functional properties. Synthetic protocols based on molecular rearrangements are often favored over traditional methods, as they can eliminate multi-step syntheses and the need for preliminary substrate functionalization, making these processes more resource-efficient and environmentally friendly. This review analyzes the development of [1,2]-aryl shift chemistry in the 21st century, including rearrangements in aromatic carbo- and heterocycles and their application in the synthesis of polyaromatic functional materials. Particular attention is paid to tandem (cascade) reactions involving, along with the cationic [1,2]-aryl shift, processes such as the Scholl cyclization or oxidative coupling of aromatic systems. In addition to deepening the fundamental understanding of acid-mediated transformations, this review paves the way for the programmable design and synthesis of polyaromatic carbo- and heterocycles, opening exciting prospects in organic synthesis and materials design. This is the first review to address various types of tandem/cascade reactions involving the cationic [1,2]-aryl shift in various aromatic/heteroaromatic systems. This review, for the first time, traces the evolution of this rearrangement from a side process in transformations such as the Friedel–Crafts reaction or Scholl cyclization into a valuable tool in organic synthesis for the tuning of the physicochemical properties of aromatic carbo- and heterocyclic compounds.

Cite: Mekeda I.S. , Balakhonov R.Y. , Shirinian V.Z.
Cationic [1,2]-aryl shift in the design of poly(hetero)aromatic systems: from structure to functional materials
Organic & Biomolecular Chemistry. 2026. DOI: 10.1039/D6OB00064A OpenAlex

Dates:

Submitted:	Jan 15, 2026
Accepted:	Mar 10, 2026
Published online:	Mar 11, 2026

Identifiers:

≡ OpenAlex:

W7134947391

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