Reaction of singlet oxygen with the naphthalene 1 containing a carboxylic acid side chain gave a mixture of diastereomeric hydroperoxides 2a-c. The stereoselectivity depends on the concentration of the substrate 1; the fraction of 2a increases with the increase of the concentration of 1. The reaction in non-polar benzene or at lower temperature also gave more 2a. We propose that the stereoselectivity is controlled by hydrogen-bonding association of the substrate 1 at the higher concentration of 1 and at the lower temperature. The association of the carboxylic acid side-chain may induce steric hindrance for addition of singlet oxygen to increase the stereoselectivity. Proton NMR chemical shift of 1 depends on the concentration of 1 and temperature, and this is consistent with the association of the carboxylic acid.

Elimination of chiral auxiliary of 2 was carried out under acidic conditions to give optically active hydroperoxide 3 (up to 94% enantiomeric excess). Stereoselective reaction of 2 with siloxyalkenes also gave perlactone and perhemiacetal as optically active form.

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