Regioselective Synthesis of 2-Hydroperoxy-2-methylene-butanoic Acid Derivatives via Photooxygenation of Tiglic Acid Derivatives

Article abstract of DOI:10.1055/s-1986-31871

Photooxygenation of (E)-2-methyl-2-butenoic acid derivatives (tiglic acid derivatives) in tetrachloromethane in the presence of catalytic amounts of tetraphenylporphine affords 3-hydroperoxy-2-methylenebutanoic derivatives in generally high yields.Acid-catalyzed cyclodehydration of the 3-hydroperoxy-2-methylenebutanoic acid thus obtained readily gives 5-methyl-4-methylene-3-oxo-1,2-dioxolane, a peroxylactone, in 61percent yield.The analogous cyclodehydration of 3-hydroperoxy-2-methylenebutanal leads to the formation of 3-hydroxy-5-methyl-4-methylene-1,2-dioxolane.