American Chemical Society
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Stereoselectivity of Triplet Photocycloadditions:1 Diene−Carbonyl Reactions and Solvent Effects

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journal contribution
posted on 1998-05-20, 00:00 authored by Axel G. Griesbeck, Stefan Buhr, Maren Fiege, Hans Schmickler, Johann Lex
The diastereoselectivity of the photocycloaddition of benzaldehyde to furan was determined (exo/endo = 212:1) and compared with the reaction of other carbonyl compounds and carbonyl analogues. These results were compared with Paternò−Büchi reactions of cycloalkenes and cyclic enol ethers. An increase in steric demand of the α-substituent in benzoyl compounds led to a change in exo/endo-selectivity for furan cycloadditions that was not observed for cycloalkenes or cyclic enol ethers. Different ISC-reactive conformers with enhanced spin−orbit coupling are postulated as a reasonable explanation for the stereoselectivities observed. Additionally, solvent effects were studied, demonstrating the influence of photoinduced electron-transfer steps on the regio- and diastereoselectivity of Paternò−Büchi reactions with 2,3-dihydrofuran in polar solvents. Two bicyclic oxetanes (8 and 10) were characterized by X-ray structure analysis.