Syntheses of the Sex-Attractant of Pine Sawflies

Kikukawa, T.; Imaida, Motomasa; Tai, Akira

doi:10.1246/bcsj.57.1954

Cited by 29 publications

(12 citation statements)

References 14 publications

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“…The C skeleton of 3 was further constructed using a series of conversions that did not affect the asymmetric center. These were regiospecific Baeyer-Villager oxidation of saturated ketone 9 to the isopropyl ester (10), saponification to acid 11, and conversion of it to the desired bromide 3 using a Hunsdiecker reaction [4]. The overall yield of 3 was 24% calculated from starting 4.…”

Section: Synthon In the Synthesis Of (Sss)-diprionylacetate From Lmentioning

confidence: 99%

Synthesis of 3S-methylundec-1-ylbromide, a key synthon in the synthesis of (S,S,S)-diprionylacetate, from L-(-)-menthol

Ishmuratov

Yakovleva

Ganieva³

et al. 2006

Chem Nat Compd

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Section: Synthon In the Synthesis Of (Sss)-diprionylacetate From Lmentioning

confidence: 99%

Synthesis of 3S-methylundec-1-ylbromide, a key synthon in the synthesis of (S,S,S)-diprionylacetate, from L-(-)-menthol

Ishmuratov

Yakovleva

Ganieva³

et al. 2006

Chem Nat Compd

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“…The solid was chromatographed (SiO 2 , hexane) to afford 12 (1.18 g, 85%), [α] D 23 +4.02° (c 4.4, hexane), lit. [5] [α] D 21 +4.04° (c 4.5, hexane). IR and PMR spectra were identical to those in the literature [5].…”

Section: S-methylhexanal (5)mentioning

confidence: 99%

“…[5] [α] D 21 +4.04° (c 4.5, hexane). IR and PMR spectra were identical to those in the literature [5].…”

Section: S-methylhexanal (5)mentioning

confidence: 99%

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L-(-)-Menthol in the Synthesis of Key Synthons for Optically Active Methyl-Branched Insect Pheromones

et al. 2005

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A synthesis of optically active 4S-methylhexanal, 1-bromo-3S-methylheptane, and 1-bromo-3S-methylundecane, which are key synthons for several methyl-branched insect pheromones, that is based on chemically selective transformations of 6-tosyloxy-and 6-iodoisopropyl-4R-methylhexanoates that are available from L-(-)-menthol was proposed.Key words: L-(-)-menthol, 6-tosyloxy-and 6-iodoisopropyl-4R-methylhexanoates, 4S-methylhexanal, 1-bromo-3S-methylheptane, 1-bromo-3S-methylundecane, insect pheromones, synthon, synthesis.We previously reported the synthesis of chiral synthons 6-tosyloxy-(2) and 6-iodo-(3) isopropyl-4R-methylhexanoates from L-(-)-menthol (1) [1]. These were used in the present work to synthesize optically pure 4S-methylhexanal (5), 1-bromo-3S-methylheptane (11), and 1-bromo-3S-methylundecane (12), which are key intermediates for the alarm pheromone of ants of the Cremotogaster and Myrmica genera (6), sex pheromones of the peach leafminer Lyonetia clerkella (13), and pine sawflies of the Diprion and Neodiprion genera (14), respectively. The syntheses of these were also reported [2].In order to prepare 4S-methylhexanal (5), tosyloxyester 2 was converted by hydride reduction, which occurred at both esters, into 4S-methylhexan-1-ol (4), which was oxidized further by the Corey method. The resulting aldehyde (5) was transformed into the pheromone (6) by the literature method [3].Compounds 11 and 12 were synthesized using catalyzed cross-coupling of the iodoester (3) with Grignard reagents 7 and 8, which were generated from ethyl-or n-hexylbromides, to give the isopropyl ester of 4S-methyloctanoic (9) or 4S-methyldodecanoic (10) acid, respectively. Alkaline hydrolysis of esters 9 and 10 with subsequent Hunsdiecker reaction of the resulting acids produced 1-bromo-3S-methylheptane (11), which was converted to the sex pheromone of the peach leafminer (13) as before [4], and 1-bromo-3S-methylundecane (12), a key synthon for the sex pheromone of pine sawflies (14) [5], respectively.Thus, the proposed synthesis of optically pure 4S-methylhexanal, 1-bromo-3S-methylheptane, and 1-bromo-3S-methylundecane, which are key synthons for several methyl-branched insect pheromones, is based on chemically selective transformations of 6-tosyloxy-and 6-iodoisopropyl-4R-methylhexanoates, which are available from L-(-)-menthol.

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“…For example, the asymmetric reduction of keto esters by bakers' yeast has been widely used to obtain chiral compounds, because the produced hydroxy esters are useful chiral building blocks for the synthesis of natural and bioactive compounds. [7][8][9] Furthermore, several yeast keto ester reductases (YKERs) were isolated from bakers' yeast and their enzymatic properties studied including the speciˆc activity, stereoselectivity, and kinetic parameters. [10][11][12][13][14] Other microorganisms such as Thermoanaerobactor brockii, 15) Geotrichum candidum, 16,17) and Klebsiella pneumoniae 18) that can also catalyze the asymmetric reduction of keto esters are also used for the preparation of chiral hydroxy esters.…”

mentioning

confidence: 99%

Purification and Characterization of Two α-Keto Ester Reductases fromStreptomyces thermocyaneoviolaceusIFO 14271

Yamaguchi

Nakajima²,

Ishihara

2002

Bioscience, Biotechnology, and Biochemistry

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Two NADPH-dependent a-keto ester reductases (Streptomyces thermocyaneoviolaceus keto ester reductase, STKER-II and -III) were puriˆed from S. thermocyaneoviolaceus IFO 14271, one of thermophilic actinomycetes. The molecular masses of native STKER-II and -III were estimated to be 60 kDa and 70 kDa by gel ltration chromatography, respectively. These enzymes were both homodimers, with 29-kDa and 30-kDa subunit molecular masses based on SDS polyacrylamide gel electrophoresis. STKER-II and -III were stable from pH 7.0 to 10.0 and pH 5.5 to 9.0, respectively. Ethyl 3-methyl-2-oxobutanoate was reduced by both enzymes isolated to the corresponding (R)-hydroxy ester with excellent enantiomeric excess. STKER-III showed high stereoselectivity for the reduction of bulky substrates, while the selectivity of the STKER-II-catalyzed reduction was low except for ethyl 3-methyl-2-hydroxybutanoate. Both enzymes had small K m values toward aliphatic keto esters having a long alkyl chain.

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Syntheses of the Sex-Attractant of Pine Sawflies

Cited by 29 publications

References 14 publications

Synthesis of 3S-methylundec-1-ylbromide, a key synthon in the synthesis of (S,S,S)-diprionylacetate, from L-(-)-menthol

Synthesis of 3S-methylundec-1-ylbromide, a key synthon in the synthesis of (S,S,S)-diprionylacetate, from L-(-)-menthol

L-(-)-Menthol in the Synthesis of Key Synthons for Optically Active Methyl-Branched Insect Pheromones

Purification and Characterization of Two α-Keto Ester Reductases fromStreptomyces thermocyaneoviolaceusIFO 14271

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