Singlet and triplet photocycloaddition reactions of 2-pyridones with propenoate and 2,4-pentadienotes,and the frontier molecular orbital analysis

Regioselective photocycloadditions of 2-pyridones ( 1 ) with 2,4-pentadienoates ( 3 ) were analysed and compared with the reactions with propenoate ( 2 ), and origins of the different regioselectivities were inferred from frontier molecular orbital properties by the use of PM3-CI method. Direct photoreactions of 1 with 3 being α,β,γ,δ-unsaturated carboxylates gave four types of regio-selective 2+2]cycloadducts, 3-β:4-α-4, 5, 3-δ:4-γ-6,7,5-δ: 6-γ-8, 9 and 5-δ:6-γ-2+2]cycloadducts 10,11. Sensitized photoreactions of 1 with 3 did not occur, and fluorescence of 1 was weakly quenched by 3. Otherwise, main cycloadducts in the sensitized reactions of 1 with 2 have been obtained as 5-α:6-β-2+2]cycloadducts, which were different from main 3-β:4-α-2+2]cycloadducts of the direct reactions, and these site-and regio-selectivities were inferred from the different frontier molecular orbital coefficients at the. 3-and 6-positions of 1 for the triplet and singlet states. Formations of 4–7 were also interpreted by both effects of frontier orbital HSOMO-LUMO interactions and of the electrostatic interaction between 1 and 3. The other site-and regioselective adducts 8–11 were inferred to be formed by the electrostatic interactions similar to 2-pyridone photodimerization.