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Issue 5, 2018
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Guiding a divergent reaction by photochemical control: bichromatic selective access to levulinates and butenolides

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Abstract

Allylic and acrylic substrates may be efficiently transformed by a sequential bichromatic photochemical process into derivatives of levulinates or butenolides with high selectivity when phenanthrene is used as a regulator. Thus, UV-A photoinduced cross-metathesis (CM) couples the acrylic and allylic counterparts and subsequent UV-C irradiation initiates EZ isomerization of the carbon–carbon double bond, followed by one of two competing processes; namely, cyclization by transesterification or a 1,5-H shift and tautomerization. Quantum chemical calculations demonstrate that intermediates are strongly blue-shifted for the cyclization while red-shifted for the 1,5-H shift reaction. Hence, delaying the double bond migration by employing UV-C absorbing phenanthrene, results in a selective novel divergent all-photochemical pathway for the synthesis of fundamental structural motifs of ubiquitous natural products.

Graphical abstract: Guiding a divergent reaction by photochemical control: bichromatic selective access to levulinates and butenolides

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Publication details

The article was received on 29 Nov 2017, accepted on 18 Dec 2017 and first published on 18 Dec 2017


Article type: Edge Article
DOI: 10.1039/C7SC05094A
Citation: Chem. Sci., 2018,9, 1368-1374
  • Open access: Creative Commons BY license
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    Guiding a divergent reaction by photochemical control: bichromatic selective access to levulinates and butenolides

    Revannath L. Sutar, S. Sen, O. Eivgi, G. Segalovich, I. Schapiro, O. Reany and N. G. Lemcoff, Chem. Sci., 2018, 9, 1368
    DOI: 10.1039/C7SC05094A

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