Photochemistry of cytosine derivatives. 1. Photochemistry of thymidylyl-(3' leads to 5')-deoxycytidine

Abstract

The photochemistry of thymidylyl-(3' leads to 5')- deoxycytidine (dTpdC) was studied as a model system of adjacent thymine and cytosine bases in DNA. Acetophenonesensitized irradiation causes the cytosine moiety in dTpdC to react with the thymine moiety intramolecularly. Three unstable photoproducts are formed initially which are converted into three isomeric dinucleoside phosphates of thymine-uracil cyclobutane photodimer in a ratio of 4.2:2.2:1. Under the same irradiation condition thymidylyl-(3' leads to 5')-thymidine (dTpdT) yields two products in a ratio of 6:1. The structures of these products are established by chemical and spectroscopic methods. The major product in these reactions has been identified as the stereoisomer which has the same anti,anti relationship between the pyrimidine rings and the deoxyribose group as in the parent dinucleoside phosphates. The efficiency of the intramolecular dimerization of dTpdC is about one-third that of dTpdT. The results suggest that the cytosine base in DNA may be converted to a uracil base via photodimerization with an adjacent pyrimidine base, hydrolysis, and photoreactivation.