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Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction.
Journal article

Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction.

  • Geigle SN Department of Chemistry , University of Basel , St. Johanns-Ring 19 , CH-4056 , Basel , Switzerland . Email: dennis.gillingham@unibas.ch.
  • Wyss LA Department of Health Sciences and Technology , ETH Zurich , Schmelzbergstrasse 9 , CH-8092 Zurich , Switzerland.
  • Sturla SJ Department of Health Sciences and Technology , ETH Zurich , Schmelzbergstrasse 9 , CH-8092 Zurich , Switzerland.
  • Gillingham DG Department of Chemistry , University of Basel , St. Johanns-Ring 19 , CH-4056 , Basel , Switzerland . Email: dennis.gillingham@unibas.ch.
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  • 2017-04-29
Published in:
  • Chemical science. - 2017
General Chemistry
English 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.
Language
  • English
Open access status
gold
Identifiers
Persistent URL
https://folia.unifr.ch/global/documents/263320
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