Photosynthesis in plants has inspired photochemical reactions in organic chemistry. Synthetic organic chemists always seek cost-effective, operationally simple, averting the use of toxic and difficult-to-remove metallic catalysts, atom economical, and high product purity in organic reactions. In the last few decades, the use of light as a catalyst in organic reactions has increased exponentially as literature has exploded with examples, particularly by using toxic and expensive metal complexes, photosensitizers like organic dyes, hypervalent iodine, or by using inorganic semiconductors. In this report, we have selected a few interesting examples of photochemical reactions performed without using any metallic catalyst or photosensitizers. These examples use the inherent potential of reactants to utilize light energy to initiate chemical reactions. Our main emphasis is to highlight the structural features in the reactants that can absorb light energy or form an electron donor-acceptor (EDA) complex during the reaction to initiate the photochemical reaction. Considering the high degree of variability in the photochemical reactions, the utmost care has been taken to present the most accurate reaction conditions. A short introductory section on photochemical reactions will act as an anchor that will revolve around the examples discussed and explain the underlying principle of the photochemical reaction mechanism.
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http://dx.doi.org/10.1002/tcr.202400227 | DOI Listing |
Chem Rec
March 2025
University of Leuven, KU Leuven), LOMAC Celestijnenlaan 200F, B-3001, Leuven, Belgium.
Photosynthesis in plants has inspired photochemical reactions in organic chemistry. Synthetic organic chemists always seek cost-effective, operationally simple, averting the use of toxic and difficult-to-remove metallic catalysts, atom economical, and high product purity in organic reactions. In the last few decades, the use of light as a catalyst in organic reactions has increased exponentially as literature has exploded with examples, particularly by using toxic and expensive metal complexes, photosensitizers like organic dyes, hypervalent iodine, or by using inorganic semiconductors.
View Article and Find Full Text PDFPLoS Comput Biol
March 2025
Digital Environment Research Institute, Queen Mary University of London, London, United Kingdom.
Oxygenic photosynthesis is responsible for nearly all biomass production on Earth, and may have been a prerequisite for establishing a complex biosphere rich in multicellular life. Life on Earth has evolved to perform photosynthesis in a wide range of light environments, but with a common basic architecture of a light-harvesting antenna system coupled to a photochemical reaction centre. Using a generalized thermodynamic model of light-harvesting, coupled with an evolutionary algorithm, we predict the type of light-harvesting structures that might evolve in light of different intensities and spectral profiles.
View Article and Find Full Text PDFChemistry
March 2025
Kanazawa University, Institute for Frontier Science Initiative, Kakuma0machi, 920-1192, Kanazawa, JAPAN.
Phosphate and sulfate groups play an important role in controlling the physical properties of biomolecules and artificial materials. However, despite their significance, the incorporation of phosphate or sulfate groups into aqueous organic compounds using non-enzymatic methods has been unprecedented. In this study, we have successfully conjugated inorganic phosphate and sulfate with aminocyclobutenedione derivatives via photochemical reactions under aqueous conditions.
View Article and Find Full Text PDFJ Chem Phys
March 2025
Department of Chemistry, Kobe University, Nada-ku, Kobe, Hyogo 657-8501, Japan.
Donor-acceptor (D-A) molecules are key motifs in electron transfer processes. Recently, significant progress has been made in the development of organic synthetic reactions that utilize D-A molecules as photoredox catalysts. In these electron-transfer reactions, preventing undesired back-electron transfer and achieving efficient conversion is essential.
View Article and Find Full Text PDFJ Org Chem
March 2025
Department Chemie and Catalysis Research Center (CRC), Technische Universität München, Lichtenbergstr. 4, 85747 Garching, Germany.
4-Substituted 7-(4'-alkenyloxy)-1-indanones were prepared from the respective substituted aryl propanoic acids and subjected to UV-A irradiation (λ = 350 or 366 nm). While the 4-chloro compound was directly converted at λ = 366 nm into a pentacyclic product (47% yield) by a three-photon cascade process, the oxygenated substrates reacted in trifluoroethanol at λ = 350 nm by a two-photon cascade, involving an photocycloaddition, a thermal disrotatory ring opening, and a [4π] photocyclization (six examples, 67-82% yield). An ensuing photochemical di-π-methane rearrangement of the latter products was achieved by irradiation at λ = 350 nm in toluene (five examples, 36-70% yield).
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