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Chain propagation determines the chemo- and regioselectivity of alkyl radical additions to C–O vs. C–C double bonds

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Abstract

Investigations into the selectivity of intermolecular alkyl radical additions to C–O- vs. C–C-double bonds in α,β-unsaturated carbonyl compounds are described. Therefore, a photoredox-initiated radical chain reaction is explored, where the activation of the carbonyl-group through an in situ generated Lewis acid – originating from the substrate – enables the formation of either C–O or the C–C-addition products. α,β-Unsaturated aldehydes form selectively 1,2-, while esters and ketones form the corresponding 1,4-addition products exclusively. Computational studies lead to reason that this chemo- and regioselectivity is determined by the consecutive step, i.e. an electron transfer, after reversible radical addition, which eventually propagates the radical chain.

Graphical abstract: Chain propagation determines the chemo- and regioselectivity of alkyl radical additions to C–O vs. C–C double bonds

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Publication details

The article was received on 25 Sep 2019, accepted on 25 Nov 2019 and first published on 26 Nov 2019


Article type: Edge Article
DOI: 10.1039/C9SC04846D
Chem. Sci., 2020, Advance Article
  • Open access: Creative Commons BY-NC license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    Chain propagation determines the chemo- and regioselectivity of alkyl radical additions to C–O vs. C–C double bonds

    T. O. Paulisch, F. Strieth-Kalthoff, C. Henkel, L. Pitzer, D. M. Guldi and F. Glorius, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC04846D

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