Reversible photocycloaddition of a 4',5'-dihydropsoralen derivative with thymine.
The photocycloaddition reaction between a 4',5'-dihydropsoralen derivative and thymine was studied in solution using a synthetic bichromophoric model 8 in which the two rings are associated by a tetramethylene chain. In water this model molecule exhibits intramolecular ring-ring stacking interactions as evidenced by UV and NMR spectroscopies. Irradiation at 365 nm at usual concentrations (greater than or equal to 5.10(-4) M) leads exclusively to a regio- and stereo-selective dimerization reaction involving the 3,4 double bonds of the psoralen moities. Extreme dilutions (ca less than or equal to 2.10(-5) M) were necessary to observe the intramolecular reaction which results in the exclusive formation of a 3,4 cis-anti adduct. This reaction is completely reversed by irradiation at 254 nm. These results are discussed with regard to the behavior of the homologous models in which the furan part of the psoralen ring is not hydrogenated. These latter compounds also lead exclusively to a 3,4 cis-anti adduct. It appears that saturation of the furan ring increases strongly the quantum yield of the photoaddition at 365 nm (0.01----0.18) and that the triplet excited state of the 4',5'-dihydropsoralen is involved in the photoaddition.
Decout
J L
JL
L.E.D.S.S., Université Joseph Fourier, URA CNRS 332, Grenoble, France.
Lhomme
J
J
D011564:Furocoumarins / Q000138:chemical synthesis / Q000737:chemistry*; D007202:Indicators and Reagents; D010777:Photochemistry; D013053:Spectrophotometry; D013329:Structure-Activity Relationship; D013941:Thymine / Q000737:chemistry*
D011564:Furocoumarins; D007202:Indicators and Reagents; D013941:Thymine