The chemoselective synthesis of amides by decarboxylative couplings of alpha-ketoacids and isoxazolidines makes possible an iterative approach to poly-beta3-peptides. Peptide assembly occurs under aqueous conditions and requires no coupling reagents. The requisite isoxazolidine monomers are prepared in enantiopure form by a convenient two-step protocol starting from the appropriate aldehydes.

BACKGROUNDSemiochemicals for monitoring, attracting or repelling pest and beneficial organisms are increasingly deployed in agricultural and forest systems for pest management. However, the use of aggregation pheromones and host‐plant attractants for the express purpose of increasing the efficacy of classical biological control agents of weeds has not been widely reported. Therefore, we conducted field‐based assays to determine if a specialized wax‐based matrix impregnated with an aggregation pheromone of the northern tamarisk beetle Diorhabda carinulata (Desbrochers) or host‐plant volatiles could increase the efficacy of D. carinulata.RESULTSThe aggregation pheromone and host‐plant volatiles were formulated for field application using a wax‐based matrix. Reported release rates suggest that this matrix is a viable formulation for enhancing D. carinulata aggregations under field conditions. Pheromone‐treated saltcedar plants (Tamarix spp.) not only had higher densities of adult and larval D. carinulata, but also sustained greater levels of foliar damage than control plants. Increased damage from the focused feeding of D. carinulata caused an increase in foliar dieback and decrease in live canopy volume of semiochemical‐treated plants.CONCLUSIONField deployment of these semiochemical formulations could be useful in directing populations of D. carinulata for increased impact on Tamarix spp. © 2018 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

The northern tamarisk beetle Diorhabda carinulata (Desbrochers) was approved for release in the United States for classical biological control of a complex of invasive saltcedar species and their hybrids (Tamarix spp.). An aggregation pheromone used by D. carinulata to locate conspecifics is fundamental to colonization and reproductive success. A specialized matrix formulated for controlled release of this aggregation pheromone was developed as a lure to manipulate adult densities in the field. One application of the lure at onset of adult emergence for each generation provided long term attraction and retention of D. carinulata adults on treated Tamarix spp. plants. Treated plants exhibited greater levels of defoliation, dieback and canopy reduction. Application of a single, well-timed aggregation pheromone treatment per generation increased the efficacy of this classical weed biological control agent.

β 3 -Amino acids are key components of some pharmaceuticals, excellent surrogates for metabolically labile αamino acids, and building blocks for chiral heterocycles. Unfortunately they are not easily accessible in enantiomerically pure form, especially when possessing unnatural side chains. A flexible, chromatography-free process for the synthesis of enantiopure β 3 -amino acids possessing natural and unnatural side chains is described. The procedure uses inexpensive starting materials and reagents and offers a good alternative to the hazardous and expensive Arndt−Eistert homologation of enantiopure α-amino acids. Its utility has been demonstrated with the preparative scale synthesis of two valuable β 3 -amino acids possessing unnatural side chains.

A versatile method for the synthesis of enantiomerically pure isoxazolidine monomers for the synthesis of β3‐oligopeptides via α‐keto acidhydroxylamine (KAHA) ligation is presented. This one‐pot synthetic method utilizes in situ generated nitrones bearing gulose‐derived chiral auxiliaries for the asymmetric 1,3‐dipolar cycloaddition with methyl 2‐methoxyacrylate. The resulting enantiomerically pure isoxazolidine monomers bearing diverse side chains (proteinogenic and non‐proteinogenic) can be synthesized in either configuration (like‐ and unlike‐configured). The scalable and enantioselective synthesis of the isoxazolidine monomers enables the use of the synthesis of β3‐oligopeptides via iterative α‐keto acidhydroxylamine (KAHA) ligation.