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Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction

Geigle, Stefanie and Wyss, Laura and Sturla, Shana and Gillingham, Dennis. (2017) Copper carbenes alkylate guanine chemoselectively through a substrate directed reaction. Chemical Science, 8. pp. 499-506.

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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.
Faculties and Departments:05 Faculty of Science > Departement Chemie > Chemie > Organische Chemie (Gillingham)
UniBasel Contributors:Gillingham, Dennis
Item Type:Article, refereed
Article Subtype:Research Article
Publisher:Royal Society of Chemistry
ISSN:2041-6520
e-ISSN:2041-6539
Note:Publication type according to Uni Basel Research Database: Journal article
Language:English
Identification Number:
Last Modified:27 Feb 2017 13:10
Deposited On:27 Feb 2017 13:10

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