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Issue 12, 2016
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Stereoselective photoreaction in P-stereogenic dithiazolylbenzo[b]phosphole chalcogenides

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Abstract

Diastereoselective photocyclization reactions based on a 6π-system have been demonstrated with terarylene molecules having a P-stereogenic moiety. A chiral benzo[b]phosphole chalcogenide unit was introduced as a central bridging part in a terarylene to form a photochromic dithiazolylbenzo[b]phosphole chalcogenide. The stereoselective photoreaction of terarylenes was controlled by the conformational preference in the photoprecursor open-forms, which was dictated by the intramolecular interactions involving the chiral phosphorus atom and its substituents. Dithiazolylbenzo[b]phosphole oxide showed moderate photocyclization quantum yield and diastereoselectivity, which were significantly improved by replacing the oxygen atom with a sulfur atom showing photon-quantitative reactivity in toluene. The conformational preferences, which play an important role in the photocyclization quantum yield and diastereoselectivity, were thoroughly investigated by means of DFT calculations, X-ray crystallography, NMR measurements and circular dichroism spectra.

Graphical abstract: Stereoselective photoreaction in P-stereogenic dithiazolylbenzo[b]phosphole chalcogenides

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Publication details

The article was received on 05 Aug 2016, accepted on 10 Oct 2016 and first published on 10 Oct 2016


Article type: Paper
DOI: 10.1039/C6NJ02446G
Citation: New J. Chem., 2016,40, 10048-10055
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    Stereoselective photoreaction in P-stereogenic dithiazolylbenzo[b]phosphole chalcogenides

    S. Iijima, T. Nakashima and T. Kawai, New J. Chem., 2016, 40, 10048
    DOI: 10.1039/C6NJ02446G

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