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Mechanistic studies of UV assisted [4 + 2] cycloadditions in synthetic efforts toward vibsanin E
Joachim Nikolai1, Øystein Loe, Paulina M Dominiak
1Department of Chemistry, University at Buffalo, The State University of New York, Buffalo, New York 14260-3000, USA.
Abstract:
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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