Plant Analysis by Butterflies:  Occurrence of Cyclopentenylglycines in Passifloraceae, Flacourtiaceae, and Turneraceae and Discovery of the Novel Nonproteinogenic Amino Acid 2-(3‘-Cyclopentenyl)glycine in Rinorea

Abstract

Following records about feeding habits of nymphalid butterflies, a novel nonproteinogenic L-amino acid, (S)-2-(3'-cyclopentenyl)glycine (11), was discovered in Rinorea ilicifolia, a species where the presence of a cyclopentanoid natural product of this kind was neither known nor anticipated from the taxonomic point of view. Another novel amino acid, (2S,1'S,2'S)-2-(2'-hydroxy-3'-cyclopentenyl)glycine (12), the stereochemistry of which was determined by single-crystal X-ray diffraction, was shown to occur in species belonging to Flacourtiaceae, Passifloraceae, and Turneraceae. These species, many of which serve as hosts for nymphalid butterflies (Acraeinae, Heliconiinae, Argynninae), also produce 2-(2'-cyclopentenyl)glycine. Cyclopentenylglycines are proposed to be novel chemical recognition templates for plant-insect interactions. Ratios between the epimers of (2S)-2-(2'-cyclopentenyl)glycine, which co-occur in plants, were determined by (1)H NMR spectroscopy. Contrary to a previous report, the (2S,1'R) epimer always appears to predominate over the (2S,1'S) epimer. Stereochemical aspects of biosynthesis of natural cyclopentanoid cyanogenic glycosides are discussed in relation to these findings.

Effects of Foliar Surfactants on Host Plant Selection Behavior ofLiriomyza huidobrensis(Diptera: Agromyzidae)

“…Chemical cues present in plants are a major determinant for host plant identiÞcation in many insects, and plants that do not have the correct chemical signature may be ignored as oviposition sites (Wallin and Raffa 2000, Clausen et al 2002, Cunningham and Floyd 2004. Foliar applications of plant extracts have resulted in reduced damage to crops because of decreased oviposition by L. huidobrensis (Banchio et al 2003).…”

Methyl 2-(1,3-dioxoisoindolin-2-yl)acrylate

“…For related literature, see: Cativiela et al (2000); Clausen et al (2002); Schmidt et al (1988);Trost & Dake, (1997); Wirth (1997); Osborn et al (1966). For related structures, see: 1979); 1986).…”

“…Optical active nonproteinogenic amino acids (Clausen et al, 2002) are valuable compounds of high interest not only due to their remarkable pharmacological and biological activities but also for their role as a topographic probe for investigation of bioactive conformations of peptides and the mechanisms of enzyme reactions. Consequently, efficient and convenient methods for the preparation of optically pure enantiomers of amino acids are be general interest (Cativiela & Diaz-de-Villegas, 2000;Wirth, 1997).…”

Cyclopentanoid Cyanohydrin Glucosides and Amides ofLindackeria dentata

“…One class comprises derivatives of mandelonitrile and its hydroxylated counterparts, biosynthetically derived from phenylalanine or tyrosine; the structural diversity within this group has been explored largely by Nahrstedt et al [1], [2]. The other class includes derivatives of the aliphatic amino acids valine and isoleucine [1], [2], and the third comprises the relatively rare derivatives of the non-proteinogenic amino acid 2-cyclopentenylglycine [1], [2], [3], [4]. Biosynthesis, toxicology and ecology of cyanogenic glycosides and more recently genetic engineering of cyanogenic plants have attracted considerable interest.…”

“…In this communication, we describe cyclopentanoid cyanohydrin glucosides and cyclopentanoid amides of Lindackeria dentata (Oliv.) Gilg, a species belonging to the family Flacourtiaceae, which is characterized by a variety of natural products apparently derived from 2-cyclopentenylglycine [4], [5], [6], [7], [8].…”