Sesquiterpene lactones with potential use as natural herbicide models. 2. guaianolides.
A structure-activity study to evaluate the effect of 17 guaianolide sesquiterpene lactones (in a range of 100-0.001 microM) on the growth and germination of several mono- and dicotyledon target species is accomplished. Results are compared with those obtained in the same bioassay with an internal standard, the commercial herbicide Logran, to validate the results with a known active formulation and to compare the results with a commercial product to test their potential use as natural herbicide models. Specific conditions for the selective mono- or polyhydroxylation of guaianolides using the SeO(2)/tert-butyl hydroperoxide system are presented and discussed. The high regio- and stereoselectivities of the reaction are explained through the specific structural requirements of the bulky first adduct formed during the ene reaction. These compounds appear to have deeper effects on the growth of either monocots or dicots than the previously tested germacranolides. Otherwise, the lactone group seems to be necessary for the activity, though it does not necessarily need to be unsaturated. However, the presence of a second and easily accessible unsaturated carbonyl system greatly enhances the inhibitory activity. Lipophilicity and the stereochemistry of the possible anchoring sites are also crucial factors for the activity. Finally, the levels of growth inhibition obtained with some compounds on dicots or monocots are totally comparable to those of Logran and allow proposing them as lead compounds.
Macías
F A
FA
Departamento de Química Orgánica, Facultad de Ciencias, Universidad de Cádiz, c/ República Saharaui s/n, Apdo. 40, 11510-Puerto Real, Cádiz, Spain. famacias@uca.es
Galindo
J C
JC
Castellano
D
D
Velasco
R F
RF
D006540:Herbicides / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D007783:Lactones / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology; D018551:Solanum lycopersicum / Q000187:drug effects / Q000254:growth & development; D008958:Models, Molecular; D008968:Molecular Conformation; D015394:Molecular Structure; D010945:Plants, Edible / Q000187:drug effects* / Q000254:growth & development; D012717:Sesquiterpenes / Q000138:chemical synthesis* / Q000737:chemistry / Q000494:pharmacology*; D013329:Structure-Activity Relationship; D014675:Vegetables / Q000187:drug effects / Q000254:growth & development
D006540:Herbicides; D007783:Lactones; D012717:Sesquiterpenes