81309-89-9

Upstream product

• 81309-88-8 (2S,3R)-8-methyl-2,3-epoxynonan-1-ol 
• 98-59-9 p-toluenesulfonyl chloride 
• 115937-04-7 2,3-epoxy-8-methyl-1-nonanol 
• 145050-13-1 (2S,3R)-1-tert-Butyldiphenylsilyloxy-2,3-epoxy-8-methylnonane 
• 81309-86-6 (Z)-8-methyl-2-nonen-1-ol 
• 107996-53-2 (2S,3R)-1-(3',5'-dinitrobenzoyloxy)-2,3-epoxy-8-methylnonane 
• 124318-36-1 6-methylheptyl phenyl sulfone 
• 5026-76-6 6-methylhept-1-ene 

Downstream Products

• 54910-51-9 (2S-cis)-7,8-epoxy-2-methyloctadecane 

Relevant academic research and scientific papers

Enantiomer and conformer recognition of (+) and (-)-disparlure and their analogs by the pheromone binding proteins of the gypsy moth, Lymantria dispar

Adult female gypsy moths produce a sex pheromone (+)-(7R,8S)-2-methyl-7,8- epoxyoctadecane, (+)-disparlure, to attract male gypsy moths. To better understand the recognition of (+)-disparlure by the male's olfactory system, we synthesized racemic and enantiopure oxa and thia analogs of (+)-disparlure (ee > 98%). Ab initio calculations of the conformeric landscapes around the dihedral angles C5-6-7-8 and C7-8-9-10 of (+)-disparlure and corresponding dihedral angles of analogs revealed that introduction of the heteroatom changes the conformeric landscape around these important epitopes. The energy difference between HOMO and LUMO decreased after oxygen or sulfur was introduced into the backbone. Consistent with this, an enhancement of binding affinity between sulfur analogs and the pheromone-binding proteins (PBPs) was observed in vitro. Docking of the pheromone and analogs onto models of the two known PBPs of the gypsy moth revealed that the internal binding pocket of PBP1 showed higher selectivity than that of PBP2, consistent with in vitro binding assays. Further energy analysis revealed that enantiomers adopted different conformations with different energies when docked in the internal binding pocket of PBPs, resulting in enantiomer discrimination of PBPs towards disparlure and its analogs.

Pheromone synthesis; CXXXIX. Enzymatic preparation of (2S,3R)-4-acetoxy-2,3-epoxybutan-1-ol and its conversion to the epoxy pheromones of the gypsy moth and the ruby tiger moth

Pig pancreatic lipase-catalyzed asymmetric hydrolysis of 1,4-diacetoxy-cis-2,3-epoxybutane yielded (2S,3R)-4-acetoxy-2,3-epoxybutan-1-ol, which was converted to two naturally occurring epoxides: the gypsy moth pheromone, disparlure [(7R,8S)-7,8-epoxy-2-methyloctadecane] and the ruby tiger moth pheromone [(6Z,9S,10R)-9,10-epoxy-6-henicosene].

APPLICATION OF BIOCHEMICAL METHODS IN ENANTIOSELECTIVE SYNTHESIS OF BIOACTIVE NATURAL PRODUCTS

Enzymes as well as yeasts were used in enantioselective syntheses of bioregulators such as hormones and semiochemicals.Lipases and esterases were employed in achieving optical resolution, conversion of meso-compounds to optically active compounds, and macrolactonization.Lactase effected glucosidation of a phenolic hydroxy ketone without any protection of the functional groups.Yeasts provided a variety of optically active hydroxy esters and ketones, which served as versatile non-racemic chiral building blocks.

Synthesis of (+)-Disparlure Using the Reaction of 6-Methylheptyl Phenyl Sulfone with Trimethylsilyloxirane and Asymmetric Epoxidation

Reaction of lithiated sulfone 3 with trimethyl(oxiranyl)silane 4, followed by acid hydrolysis, afforded the (Z)-allylic alcohol 6 contaminated with its (E) isomer.Epoxidation of 6 by the Sharpless procedure yielded the hydroxy epoxide, which was isolated as its enantiomerically pure 3,5-dinitrobenzoyl derivative 7 and transformed into (+)-disparlure 1 via alcohol 8 and tosylate 9.

SYNTHESIS OF (+)-DISPARLURE USING THE REACTION OF 6-METHYLHEPTYL PHENYL SULPHONE WITH TRIMETHYLSILYL ETHYLENE OXIDE AND ASYMMETRIC EPOXIDATION

Lithiated sulphone 2 was reacted with trimethyl(oxiranyl)silane 3 to yield allylic alcohol 4; the latter was epoxidized by the Sharpless procedure and the corresponding hydroxy-epoxide 5b was transformed into (+)-disparlure 6 via tosylate 5c.

SYNTHESES OF OPTICALLY ACTIVE PHEROMONES WITH AN EPOXY RING, (+)-DISPARLURE AND BOTH THE ENANTIOMERS OF (3Z,6Z)-cis-9,10-EPOXY-3,6-HENEICOSADIENE

(+)-Disparlure 1 and both the enantiomers of (3Z,6Z)-cis-9,10-epoxy-3,6-heneicosadiene 2 were synthesized in optically pure forms employing the Sharpless asymmetric epoxidation as the key-step.The natural pheromone 2 isolated from Estigmene acrea was shown to possess (9S,10R)-stereochemistry.