54910-51-9Relevant articles and documents
Cis-epoxides via Sharpless' Asymmetric Dihydroxylation Reaction: Synthesis of (+)-Disparlure
Ko, Soo Y.
, p. 3601 - 3604 (1994)
(+)-Disparlure, containing an isolated cis-epoxide functional group, was synthesized employing the asymmetric dihydroxylation cyclic sulfate rearrangement-opening reactions as the key steps.
Synthesis of (+)-Disparlure via Enantioselective Iodolactonization
Klosowski, Daniel W.,Martin, Stephen F.
, p. 1269 - 1271 (2018)
The BINOL-amidine organic catalyst 1 was previously shown to promote highly efficient enantioselective halolactonization reactions of olefinic acids. As part of these studies, it was discovered that the enantioenriched iodolactones could be easily convert
Synthesis of disparlure and monachalure enantiomers from 2,3-butanediacetals
Drop, Adam,Fr?ckowiak-Wojtasek, Bo?ena,Wojtasek, Hubert
, p. 616 - 620 (2020)
2,3-Butanediacetal derivatives were used for the stereoselective synthesis of unsymmetrically substituted cis-epoxides. The procedure was applied for the preparation of both enantiomers of disparlure and monachalure, the components of the sex pheromones of the gypsy moth (Lymantria dispar) and the nun moth (Lymantria monacha) using methyl (2S,3R,5R,6R)-3-ethylsulfanylcarbonyl-5,6-dimethoxy-5,6-dimethyl-1,4-dioxane-2-carboxylate as the starting material.
Synthesis of Isotopically Labelled Disparlure Enantiomers and Application to the Study of Enantiomer Discrimination in Gypsy Moth Pheromone-Binding Proteins
Pinnelli, Govardhana R.,Terrado, Mailyn,Hillier, N. Kirk,Lance, David R.,Plettner, Erika
, p. 6807 - 6821 (2019)
To study the binding mechanism of disparlure (7,8)-epoxy-2-methyloctadecane enantiomers with pheromone-binding proteins (PBPs) of the gypsy moth, oxygen-17 or 18 and 5,5,6,6-deuterium labelled disparlure enantiomers were prepared in an efficient, enantioselective route. Key steps involve the asymmetric α-chlorination of dodecanal by SOMO catalysis and Mitsunobu inversion of a 1,2-chlorohydrin. The pheromone, (+)-disparlure (7R, 8S), was tested in two infested zones, demonstrating that it is very attractive towards male gypsy moths. Studies of the binding of (+)-disparlure and its antipode to gypsy moth PBPs by 2H &17O NMR at 600 MHz are reported. Chemical shifts, spin-lattice relaxation decay times (T1) and transverse relaxation decay times (T2) of deuterium atoms of disparlure enantiomers in 2H NMR show that the binding of disparlure enantiomers to PBP1 differs from binding to PBP2, as expected from their opposite binding preferences (PBP1 binds (–)-disparlure, and PBP2 binds (+)-disparlure more strongly). Models of the disparlure enantiomers bound to one internal binding site and two external binding sites of both PBPs were constructed. The observed chemical shift changes of deuterated ligand signals, from non-bound to bound, T1 and T2 values are correlated with results from the simulations. Together these results suggest that the disparlure enantiomers adopt distinct conformations within the binding sites of the two PBPs and interact with residues that line the sites.
A short and efficient synthesis of (+)-disparlure and its enantiomer
Koumbis, Alexandros E.,Chronopoulos, Demetrios D.
, p. 4353 - 4355 (2005)
A short and highly efficient approach was applied for the total synthesis of the gypsy moth sex pheromone (+)-disparlure and its enantiomer from isopropylidene D- and L-erythrose, using a common strategy.
Enantioselective Halolactonization Reactions using BINOL-Derived Bifunctional Catalysts: Methodology, Diversification, and Applications
Klosowski, Daniel W.,Hethcox, J. Caleb,Paull, Daniel H.,Fang, Chao,Donald, James R.,Shugrue, Christopher R.,Pansick, Andrew D.,Martin, Stephen F.
, p. 5954 - 5968 (2018/05/15)
A general protocol is described for inducing enantioselective halolactonizations of unsaturated carboxylic acids using novel bifunctional organic catalysts derived from a chiral binaphthalene scaffold. Bromo- and iodolactonization reactions of diversely substituted, unsaturated carboxylic acids proceed with high degrees of enantioselectivity, regioselectivity, and diastereoselectivity. Notably, these BINOL-derived catalysts are the first to induce the bromo- and iodolactonizations of 5-alkyl-4(Z)-olefinic acids via 5-exo mode cyclizations to give lactones in which new carbon-halogen bonds are created at a stereogenic center with high diastereo- and enantioselectivities. Iodolactonizations of 6-substituted-5(Z)-olefinic acids also occur via 6-exo cyclizations to provide δ-lactones with excellent enantioselectivities. Several notable applications of this halolactonization methodology were developed for desymmetrization, kinetic resolution, and epoxidation of Z-alkenes. The utility of these reactions is demonstrated by their application to a synthesis of precursors of the F-ring subunit of kibdelone C and to the shortest catalytic, enantioselective synthesis of (+)-disparlure reported to date.
