54910-51-9Relevant academic research and scientific papers
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.
Domino recombinant γ-isomerization and reverse Wacker oxidation of γ-vinyl-γ-butyrolactone: Synthesis of (+)-trans-, (-)- and (+)-disparlures
Bethi, Venkati,Kattanguru, Pullaiah,Fernandes, Rodney A.
, p. 3249 - 3255 (2014)
A domino palladium-catalyzed recombinant γ-isomerization and reverse Wacker oxidation of γ-vinyl-γ-butyrolactone has been explored. The strategy has been used in the stereoselective synthesis of (+)-trans-, (-)- and (+)-disparlures. The synthesis was achieved in seven to eight steps from D-glucono-δ-lactone with overall yields of 19.3, 20.7 and 22.6 %, respectively. Copyright
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.
Synthesis of All Four Isomers of Disparlure Using Osmium-Catalyzed Asymmetric Dihydroxylation.
Keinan, Ehud,Sinha, Subhash C.,Sinha-Bagchi, Anjana,Wang, Zhi-Min,Zhang, Xiu-Lian,Sharpless, K. Barry
, p. 6411 - 6414 (1992)
(+)-Disparlure, the sex attractant emitted by the female gypsy moth, Porthetria dispar (L.), and its (-)-enantiomer were synthesized in 43percent yield and >99percent ee, starting from undecanal and using the asymmetric dihydroxylation (AD) reaction.Similarly, the two trans-isomers of disparlure were synthesized in 51percent yield and 95percent ee.
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.
Synthesis method of gypsy moth sex pheromone
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, (2020/07/13)
The invention belongs to the technical field of chemical synthesis, and particularly relates to an efficient synthesis method of gypsy moth sex pheromone. According to the synthesis method of gypsy moth sex pheromone, silica gel immobilized ionic liquid is added as a catalyst in the step of asymmetric epoxidation based on an existing synthesis method, so that the Sharpless reaction is effectivelypromoted, the product synthesis rate in the step is increased from 60% to 85%, the synthesis rate of the whole reaction process is further greatly increased, and the synthesis efficiency of the gypsymoth sex pheromone is effectively improved.
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.
Enantioselective total synthesis of cis-(+)- and trans-(+)-disparlure
Garg, Yuvraj,Kumar Tiwari, Anand,Kumar Pandey, Satyendra
, p. 3344 - 3346 (2017/08/02)
An expedient enantioselective synthetic approach for the gypsy moth sex-attractant pheromone cis-(+)-1 and trans-(+)-disparlure 2 is described employing the optimized combination of organocatalytic MacMillan's self aldol reaction, Wittig olefination, regioselective ring opening of an epoxide and Mitsunobu esterification reactions as key steps.
