Solid-state photochemical reaction of multisubstituted thymine derivatives

Akihiro Udagawa, Priscilla Johnston, Hidehiro Uekusa, Hideko Koshima, Kei Saito, Toru Asahi

    Research output: Contribution to journalArticle

    3 Citations (Scopus)

    Abstract

    Solid-state photochemical reactions in crystals, known as topochemical reactions, are solvent-free green chemical reactions that produce stereospecific molecules. The photoreaction of thymine is interesting because the dimeric photoproduct can form four types of stereoisomers and when the dimer is formed in DNA helices it can cause skin cancers. We investigated the photoreaction of five multisubstituted thymine derivatives in the solid-state, which were designed with crystal engineering concepts to promote π-π stacking of benzene rings in the crystal. Powder X-ray diffraction analysis revealed that a para-substituted bis-thymine derivative was aligned along the c axis in the crystal and was susceptible to topochemical reaction to form a polymer, as previously reported. Ortho- and meta-substituted bis-thymine derivatives and a tetrakis-substituted derivative were found to be topochemically unreactive using both gel permeation chromatography (GPC) and X-ray crystal structural analysis. The tris-substituted thymine derivative was found to be topochemically reactive due to favorable crystal packing, which included ethanol molecules to form hydrogen bonding with one of the thymine moieties and stabilize the crystal packing. GPC and crystal structural analysis revealed that it could form tetramer at most via topochemical [2+2]-cycloaddition upon UV irradiation. Based on the crystal structure of the tris-substituted thymine derivative, the structure of the tetrameric photoproduct is expected to link via cis-syn, trans-anti and cis-syn cyclobutane isomers.

    Original languageEnglish
    Pages (from-to)6107-6114
    Number of pages8
    JournalACS Sustainable Chemistry and Engineering
    Volume4
    Issue number11
    DOIs
    Publication statusPublished - 2016 Nov 7

    Fingerprint

    Thymine
    Photochemical reactions
    crystal
    Derivatives
    Crystals
    Gel permeation chromatography
    Structural analysis
    structural analysis
    chromatography
    Crystal engineering
    Cyclobutanes
    gel
    Molecules
    Stereoisomerism
    Cycloaddition
    solid state
    photochemical reaction
    Benzene
    Isomers
    Dimers

    Keywords

    • Green chemistry
    • Organic crystals
    • Photochemical reaction
    • Solid-state reaction
    • Thymine

    ASJC Scopus subject areas

    • Chemistry(all)
    • Environmental Chemistry
    • Chemical Engineering(all)
    • Renewable Energy, Sustainability and the Environment

    Cite this

    Solid-state photochemical reaction of multisubstituted thymine derivatives. / Udagawa, Akihiro; Johnston, Priscilla; Uekusa, Hidehiro; Koshima, Hideko; Saito, Kei; Asahi, Toru.

    In: ACS Sustainable Chemistry and Engineering, Vol. 4, No. 11, 07.11.2016, p. 6107-6114.

    Research output: Contribution to journalArticle

    Udagawa, Akihiro ; Johnston, Priscilla ; Uekusa, Hidehiro ; Koshima, Hideko ; Saito, Kei ; Asahi, Toru. / Solid-state photochemical reaction of multisubstituted thymine derivatives. In: ACS Sustainable Chemistry and Engineering. 2016 ; Vol. 4, No. 11. pp. 6107-6114.
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