Molecular mechanism of enzymatic allene oxide cyclization in plants

Jasmonates, a collective term combining both jasmonic acid (JA) and related derivatives, are ubiquitously distributed in the plant kingdom. They are characterized as lipid-derived signal molecules which mediate a plethora of physiological functions, in particular stress responses, male fertility, and a multitude of developmental processes. In the course of JA biosynthesis, the first oxylipin with signal character, cis-(+)-12-oxo-phytodienoic acid (OPDA), is produced in a cyclization reaction catalyzed by allene oxide cyclase (AOC). This enzyme-catalyzed ring closure is of particular importance, as it warrants the enantiomeric structure at the cyclopentenone ring which in the end results in the only bioactive JA enantiomer, cis-(+)-JA. In this review, we focus on the structural and molecular mechanisms underlying the above mentioned cyclization reaction. In this context, we will discuss the crystal structure of AOC2 of Arabidopsis thaliana with respect to putative binding sites of the instable substrate, 12,13-epoxy-9(Z),11,15(Z)-octadecatrienoic acid (12,13-EOT), as well as possible intermolecular rearrangements during the cyclization reaction.