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Updated: May 16, 2026

Photogeneration of N-Heterocyclic Carbenes: Application in Photoinduced Ring-Opening Metathesis Polymerization
Published on: November 29, 2018
Energy transfer (EnT)-mediated [2 + 2] photocycloadditions
1Department of Chemistry, Rishi Bankim Chandra College for Women, Naihati, 24-Parganas (N), 743165, India. suvenchem@yahoo.co.in.
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The [2 + 2] cycloaddition of alkenes is thermally forbidden and traditionally achieved through high-energy UV irradiation. However, recent advances in triplet energy transfer (EnT) enable these cycloadditions under visible light, offering mild, selective and sustainable access to cyclobutane scaffolds. With an emphasis on the key mechanistic aspects, this review highlights recent (2022-2025) advances in energy-transfer mediated inter- and intramolecular [2 + 2] photocycloadditions of olefinic substrates with efficient strategies for the construction of cyclobutane frameworks. The intermolecular reaction section is categorized into alkene-alkene [2 + 2] cycloadditions, alkene-heterocycle [2 + 2] cycloadditions, and aza-/thia-Paternò-Büchi reactions. The intramolecular reaction section is subdivided into [2 + 2] cycloadditions involving hetero-/carbocycles and acyclic analogues. In addition, recent EnT-mediated [2π + 2σ] cycloadditions are discussed, exploring new opportunities to activate strained substrates.
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Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
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