Atom Transfer Radical Addition and Cyclization in Organic Synthesis

Atom transfer radical addition (ATRA) and its cyclization variant (ATRC) have emerged as powerful tools in contemporary organic synthesis, enabling the efficient construction of carbon–halogen bonds and the rapid assembly of complex molecular architectures. These processes rely on the controlled generation of radical intermediates, often mediated by transition‐metal catalysts or visible‐light photoredox systems, to add haloalkanes across alkenes and alkynes with high regio- and stereoselectivity. Intramolecular cyclizations convert linear precursors into cyclic frameworks—such as lactams, lactones and carbocycles—under mild conditions and with broad functional-group tolerance. Applications span the synthesis of bioactive natural products, active pharmaceutical ingredients and functional materials. Ongoing research efforts strive to enhance catalyst sustainability, broaden substrate scope and deepen mechanistic insight, thereby advancing the global impact of ATRA and ATRC in streamlining synthetic pathways to valuable targets.

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Atom Transfer Radical Addition and Cyclization in Organic Synthesis publication trend

The graph below shows the total number of articles in atom transfer radical addition and cyclization in organic synthesis across all publications each year (not limited to Nature Index journals).

Technical terms

Atom transfer radical addition (ATRA): A radical sequence in which a halogen atom is transferred to an unsaturated bond, generating a new carbon–halogen linkage alongside radical addition.

Atom transfer radical cyclization (ATRC): An intramolecular form of ATRA that closes linear precursors into cyclic compounds via radical addition and ring closure.

Photoredox catalysis: Activation of substrates by light-excited catalysts that mediate single-electron transfer events to form radical intermediates.

Halogen bonding: A noncovalent interaction in which an electron-deficient halogen atom acts as a Lewis acid toward a Lewis base, facilitating selective bond activation.

References

1. Atom Transfer Radical Addition via Dual Photoredox/Manganese Catalytic System. Catalysts (2023).
2. Photoinduced Atom Transfer Radical Addition/Cyclization Reaction between Alkynes or Alkenes with Unsaturated α-Halogenated Carbonyls. Molecules (2021).
3. Atom Exchange Radical Cyclization: A Sustainable Synthetic Approach towards New Functionalized Targets. Applied Sciences (2024).