Mechanistic Studies of UV Assisted [4 + 2] Cycloadditions in Synthetic Efforts toward Vibsanin E

Quantum chemical DFT calculations at the B3LYP/6-31G(d) level have been used to study the
stereochemical course of the photochemical cycloaddition of enone 9 with dienes. The observed products
of this photochemically induced cycloaddition showed a stereoselectivity, which is opposite to what would
be expected by FMO considerations. The quantum chemical calculations revealed that the unusual
stereoselectivity of the reaction can be rationalized by assuming a stereospecific photochemical cis−trans
isomerization of enone 9 to trans isomer 9a followed by a thermal Diels−Alder reaction of the diene onto
the highly reactive trans enone. The photochemical reaction step involves the selective formation of a
twisted triplet intermediate, which accounts for the selectivity of the reaction.