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Issue 1, 2017
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Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction

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Abstract

Cu(I) carbenes derived from α-diazocarbonyl compounds lead to selective alkylation of the O6 position in guanine (O6-G) in mono- and oligonucleotides. Only purine-type lactam oxygens are targeted – other types of amides or lactams are poorly reactive under conditions that give smooth alkylation of guanine. Mechanistic studies point to N7G as a directing group that controls selectivity. Given the importance of O6-G adducts in biology and biotechnology we expect that Cu(I)-catalyzed O6-G alkylation will be a broadly used synthetic tool. While the propensity for transition metals to increase redox damage is well-appreciated, our results suggest that transition metals might also increase the vulnerability of nucleic acids to alkylation damage.

Graphical abstract: Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction

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Publication details

The article was received on 05 Aug 2016, accepted on 02 Sep 2016 and first published on 07 Sep 2016


Article type: Edge Article
DOI: 10.1039/C6SC03502G
Citation: Chem. Sci., 2017,8, 499-506
  • Open access: Creative Commons BY-NC license
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    Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction

    S. N. Geigle, L. A. Wyss, S. J. Sturla and D. G. Gillingham, Chem. Sci., 2017, 8, 499
    DOI: 10.1039/C6SC03502G

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