Predicted exocyclic amino group alkylation of 2'-deoxyadenosine and 2'-deoxyguanosine by the isopropyl cation.
Diisopropyltriazene in aqueous 10% acetonitrile (pH 7.0 +/- 0.4) yields N(6)-isopropyl-2'-deoxyAdo as the predominant product and N(2)-isopropyl-2'-deoxyGuo in yields comparable with the O(6) adduct in reactions with 2'-deoxyAdo and 2'-deoxyGuo, respectively. These observations are inconsistent with what is expected on the basis of the regnant hypothesis concerning factors that determine atom site selectivity in diazonium ion-mediated alkylations. An alternative explanation based on the fleeting existence of the reactive intermediates involved is consistent with these observations.
Blans
P
P
Department of Chemistry and Biochemistry, University of Maryland Baltimore County, 1000 Hilltop Circle, Baltimore, Maryland 21250, USA.
Fishbein
J C
JC
D000478:Alkylation; D000588:Amines / Q000737:chemistry; D002412:Cations; D018736:DNA Adducts / Q000737:chemistry*; D003839:Deoxyadenosines / Q000737:chemistry*; D003849:Deoxyguanosine / Q000737:chemistry*; D020005:Propanols / Q000737:chemistry*
D000588:Amines; D002412:Cations; D018736:DNA Adducts; D003839:Deoxyadenosines; D020005:Propanols; D003849:Deoxyguanosine; C058118:2'-deoxyadenosine