Novel regiochemistry in the aqueous singlet oxygen ene reactions of carboxylic acid salts: a comparison of substrate structure

The singlet oxygen (1Δg) photooxidations of angelic acid salt (1), tiglic acid salt (2), 2,3-dimethyl-2-butenoic acid salt (3), 3-ethoxycarbonyl-5,6-dihydro-2-methyl-4H-pyrane acid salt (4), cis-3-hexenoic acid salt (5), and trans-3-hexenoic acid salt (6) were conducted in deuterated water. The major and minor ene allylic hydroperoxide products were quantified and indicate that the allylic hydrogen geminal to the carboxylate group is preferentially abstracted in 1–4, whereas the allylic hydrogen α to the carboxylate is slightly favored for 5 and 6. We have attributed the observed regiochemistry in 1–4 to stabilizing hydrogen bonding interactions between the solvent and the perepoxide, which leads to the major ene product.