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

Authors: Joachim Nikolai , Øystein Loe , Paulina M. Dominiak , Oksana O. Gerlitz , Jochen Autschbach, and Huw M. L. Davies

J. Am. Chem. Soc.,

2007, 129 (35), 10763–10772


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.

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