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Issue 19, 2019
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Photoredox Ni-catalyzed peptide C(sp2)–O cross-coupling: from intermolecular reactions to side chain-to-tail macrocyclization

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Abstract

Ni/photoredox (4DPAIPN) dual catalysis enabled challenging peptide C(sp2)–O coupling reactions. Successful cross-coupling reactions were demonstrated with highly functionalized alcohols including side chains of amino acids (i.e., serine, threonine, tyrosine), trans-4-hydroxy-L-proline, alkyl alcohols, alkynylated alcohols, and carbohydrates. Coupling reactions between bromobenzoyl-capped peptides containing various side chains and either a protected serine building block or a serine-containing dipeptide also proceeded efficiently. Chemoselective C–O coupling (over C–N) was achieved in intermolecular reactions in the presence of a C-terminal primary amide. Furthermore, by judicious structural design in combination with computational modeling, we demonstrated side chain-to-tail macrocyclization of peptides containing a β-turn motif via C–O coupling. The methodology developed in this work brings new opportunities for late-stage diversification of complex linear and macrocyclic peptides.

Graphical abstract: Photoredox Ni-catalyzed peptide C(sp2)–O cross-coupling: from intermolecular reactions to side chain-to-tail macrocyclization

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Publication details

The article was received on 08 Feb 2019, accepted on 08 Apr 2019 and first published on 12 Apr 2019


Article type: Edge Article
DOI: 10.1039/C9SC00694J
Chem. Sci., 2019,10, 5073-5078
  • 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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    Photoredox Ni-catalyzed peptide C(sp2)–O cross-coupling: from intermolecular reactions to side chain-to-tail macrocyclization

    H. Lee, N. C. Boyer, Q. Deng, H. Kim, T. K. Sawyer and N. Sciammetta, Chem. Sci., 2019, 10, 5073
    DOI: 10.1039/C9SC00694J

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