Abstract

Allene oxides are unstable epoxides formed by the enzymatic dehydration of the lipoxygenase products of polyunsaturated fatty acids. The allene oxide synthases are of two structurally-unrelated types. In plants, a subfamily of cytochromes P450, designated as CYP74A, use the hydroperoxides of linoleic and linolenic acids as substrate. Both the 9- and 13-hydroperoxides may be converted to allene oxides and subsequently give rise to plant signaling molecules. In corals, a catalase-related hemoprotein functions as the allene oxide synthase. These marine invertebrates, as well as starfish, form allene oxides from the 8R-hydroperoxide of arachidonic acid. The coral allene oxide synthase from Plexaura homomalla occurs as the N-terminal domain of a natural fusion protein with the 8R-lipoxygenase that forms its substrate. This enzyme may be involved in biosynthesis of the cyclopentenone eicosanoids such as the clavulones.