The hydroxamic acid pathway.

Abstract

An important component of general defence mechanisms of plants are toxic secondary metabolites that function as natural pesticides. The cyclic hydroxamic acids DIBOA (2,4-dihydroxy-1,4-benzoxazin-3-one) and DIMBOA (2,4-dihydroxy-7-methoxy-1,4-benzoxazin-3-one) play an important role in the chemical defence of cereals against pests such as insects and pathogenic fungi and bacteria. Five genes that are clustered on chromosome four are sufficient to encode the enzymes to synthesize DIBOA. The first gene in the pathway, Bx1, encodes an enzyme resembling a tryptophan synthase alpha subunit that catalyses the formation of indole and thereby establishes the branchpoint that leads to the secondary metabolites. Four cytochrome P450-dependent monooxygenases encoded by Bx2-Bx5 catalyse consecutive hydroxylations to form DIBOA. This pathway can be generalized for grasses, since identical enzyme activities have been found in rye. The pathway is relatively short and begins with a metabolite ubiquitous to plants. Therefore DIBOA biosynthesis could be introduced into other plant species to confer improved disease resistance.