89102-35-2Relevant academic research and scientific papers
Intramolecular S(N)2 ring opening of a cyclic sulfate: Synthesis of erythro-(-)-6-acetoxy-5-hexadecanolide - a major component of mosquito oviposition attractant pheromone
Lohray, Braj B.,Venkateswarlu
, p. 633 - 638 (1997)
Methyl trans-hexa-5-decenoate is dihydroxylated using AD-mix-α followed by treatment with thionyl chloride to furnish cyclic sulfite 8 as the major product. The cyclic sulfate 8 is oxidized to the cyclic sulfate 2. Highly regio- and stereospecific ring opening of (4S,5S)-carboxybutyl-5-decylcyclic sulfate generated in situ by the hydrolysis of 2 furnished (5R,6S)-6-hydroxy-5-hexadecanolide 9 in high yield. Acetylation of 9 afforded natural oviposition attractant pheromone 1 in good yield.
Enantioselective synthesis of mosquito oviposition pheromone and its epimer from a naturally occurring fatty acid
Hurem, David,Dudding, Travis
, p. 101732 - 101739 (2015/12/08)
The synthesis of Mosquito Oviposition Pheromones (MOP) (5R,6S)-5-acetoxy-6-hexadecanolide and its unnatural (5R,6R)-diastereomer in 68% and 54% overall yield by a route involving an organocatalyzed epoxidation of naturally occurring cis-5-hexadecenoic acid and diastereodivergent esterification is reported. The investigation of a dynamic kinetic asymmetric transformation (DYKAT) as an alternate strategy for preparing the target MOPs is also discussed, however this approach was unsuccessful due to the formation of a ketone by-product that inhibited the lipase mediated acetylation step of the DYKAT process.
Asymmetric total synthesis of all four isomers of 6-acetoxy-5- hexadecanolide: The major component of mosquito oviposition attractant pheromones
Dong, Hong-Bo,Yang, Ming-Yan,Zhang, Xiao-Teng,Wang, Ming-An
, p. 610 - 616 (2014/05/20)
An asymmetric total synthesis of (5S,6R)-(+)-erythro-6-acetoxy-5- hexadecanolide 1a has been accomplished from readily available hex-5-yn-1-ol via Shi's asymmetric epoxidation as the key step, in eight steps with an overall yield of 33.5%. In addition, the stereoselective synthesis of all four isomers of 6-acetoxy-5-hexadecanolide 1a-1d were obtained via Sharpless asymmetric dihydroxylation and Mitsunobu reaction as the key steps with overall yields of 16.5-21.2%, respectively.
Syntheses of 5-hexadecanolide, 6-acetoxy-5-hexadecanolide and tanikolide
Chang, Meng-Yang,Lin, Chien-Lun,Chen, Shui-Tein
, p. 787 - 794 (2007/10/03)
Total syntheses of 5-hexadecanolide (1), 6-acetoxy-5-hexadecanolide (2) and tanikolide (3) are described. 1-Bromoundecane (4) and 5-benzyl-1-pentanal (5) were chosen as starting materials. Wittig olefination and Grignard addition 4 and 5 afforded the 16-carbon skeleton, which underwent a series of functional group transformations to give δ-lactone derivatives 1, 2 and 3.
Production of (5R,6S)-6-acetoxy-5-hexadecanolide, the mosquito oviposition pheromone, from the seed oil of the summer cypress plant, Kochia scoparia (Chenopodiaceae)
Olagbemiro, Timothy O.,Birkett, Michael A.,Mordue, A. Jennifer,Pickett, John A.
, p. 3411 - 3415 (2007/10/03)
The oviposition pheromone for the pathogen-vectoring mosquitoes in the genus Culex (Diptera: Culicidae), that is, (5R,6S)-6-acetoxy-5- hexadecanolide, is efficiently synthesized, in admixture with the inactive (5S,6R) enantiomer (~33% w/w), from the fixed oil extracted from the seeds of the summer cypress plant, Kochia scoparia (Chenopodiaceae), cultivated on an industrial scale. Oviposition bioassays using gravid females of Culex quinquefasciatus, a vector of filariasis in human beings, showed that the product was attractive, with activity comparable to that of a pure synthetic sample containing the same amount of the active enantiomer. Production of the pheromone in the form of a biologically active crude material via a cheap and renewable plant suitable for development as a new industrial crop provides the basis for control of Cx. quinquefasciatus and other congeneric vectors of pathogens in resource-poor areas of the world.
Enzymes in organic synthesis. 27: Lipase-catalyzed synthesis of (5R,6S)-6-acetoxyalkan-5-olides - Homologues of the mosquito oviposition attractant pheromone
Henkel,Kunath,Schick
, p. 434 - 440 (2007/10/03)
Sixteen homologous (5R*,6S*)-6-hydroxyalkan-5-olides rac-5 and their acetoxy derivatives rac-6 were synthesized from the corresponding methyl (Z)-alk-5-enoates 3 by osmium(VIII) oxide catalyzed cis-hydroxylation to the dihydroxy esters rac-4 and hydrolysi
Enzymes in Organic Synthesis, 23. - Chemo-Enzymatic Synthesis of (5R,6S)-6-Acetoxyhexadecan-5-olide - The Major Component of The Mosquito Oviposition Attractant Pheromone
Henkel, Birgitta,Kunath, Annamarie,Schick, Hans
, p. 921 - 924 (2007/10/02)
The methyl ester rac-4a of (5R*,6S*)-5,6-dihydroxyhexadecanoic acid was prepared by a Wittig reaction of (4-carboxybutyl)triphenylphosphonium bromide (2) with undecanal (1) followed by esterification with methanol and cis dihydroxylation with osmium(VIII) oxide / N-methylmorpholine N-oxide.After conversion of the dihydroxy ester rac-4a into (5R*,6S*)-6-hydroxyhexadecan-5-olide (rac-5) by lactonization (5R,6S)-6-acetoxyhexadecan-5-olide (6), the mosquito oviposition attractant pheromone, was obtained by an enantioselective lipase-catalyzed acetylation with vinyl acetate.In an alternative route the dihydroxy ester rac-4a was subjected to a lipase-catalyzed lactonization, which afforded as the main product (5S,6R)-6-hydroxyhexadecan-5-olide (ent-5), the enantiomer of the deacetylated pheromone. - Key Words: 5,6-Dihydroxyhexadecanoic acid derivatives / δ-Lactones / Resolution, kinetic / Lipases / Mosquito pheromone / Pheromones
5-Formyl-δ-valerolactone: A useful synthon for the chiral synthesis of the vespa Orientalis pheromone and the mosquito oviposition attractant pheromone
Coutrot Ph.,Grison,Bomont
, p. 8381 - 8384 (2007/10/02)
A synthetic scheme starting from the reaction between the lithiated N-allyl-N-methyl(bisdimethylamino)phosphoramide anion and the triflate derivative of (R)-(-)- or (S)-(+)-2,3-O-isopropylideneglycerol is described to prepare the key chiral synthon (R)-5- or (S)-5-formyl-δ-valerolactone that leads to the title compounds.
Oxidative Grob Fragmentation of γ-Tributylstannyl Alcohols with a Combination of Iodosylbenzene, Dicyclohexylcarbodiimide, and Boron Trifluoride
Ochiai, Masahito,Ukita, Tatsuzo,Iwaki, Shigeru,Nagao, Yoshimitsu,Fujita, Eiichi
, p. 4832 - 4840 (2007/10/02)
Exposure of cyclic γ-stannyl alcohols, prepared from cyclic vinyl ketones, to a combination of iodosylbenzene, dicyclohexylcarbodiimide, and boron trifluoride-diethyl ether in dichlorometane undergoes an oxidative Grob fragmentation to give unsaturated carbonyl compounds.The dicyclohexylcarbodiimide in this reaction apparently activates iodosylbenzene and decreases Lewis acidity of boron trifluoride.The fact that the iodine(III)-mediated Grob fragmentation proceeds stereospecifically suggests the fragmentation is concerted.The fragmentation, combined with conjugate addition of (tributylstannyl)lithium and reduction or alkylation, offers an efficient procedure for the reductive and alkylative ring opening of cyclic vinyl ketones.Since cis-benzyl ether 36, after quenching of the reaction mixture with aqueous NH4Cl, afforded the chlorostannane 37, the reaction mechanism involving the formation of iodine(III) species 32 with two oxygen ligands at iodine proposed.
REGIO- AND DIASTEREOSELECTIVITY IN ALDOL REACTIONS OF CYCLOPENT-2-ENONE, 2-(5H)FURANONE AND THEIR DERIVED TRIMETHYLSILYLOXYDIENES
Brown, David W.,Campbell, Malcolm M.,Taylor, Anthony P.,Zhang, Xiao-an
, p. 985 - 988 (2007/10/02)
Differences in erythro/threo-selectivity were assessed for aldol condensations of aldehydes with the lithium salts of cyclopent-2-enone, 2-(5H)furanone, and for Lewis acid catalysed condensation with the derived trimethylsilyloxydienes.
