Pheromone Synthesis, CLXXVIII. – Synthesis of (−)‐exo‐Isobrevicomin and Its (−)‐endo Isomer, the Components of The Male‐Produced Volatiles of the Mountain Pine Beetle, Dendroctonus ponderosae

Mori, Kenji; Takikawa, Hirosato; Nishimura, Yutaka; Horikiri, Hiromasa

doi:10.1002/jlac.199719970209

Cited by 16 publications

(10 citation statements)

References 7 publications

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“…We therefore synthesized both (1S,5R,7S)-17 and (1S,5R,7R)-21 as summarized in Scheme 3. 20 Sharpless asymmetric dihydroxylation of 15 with AD-mix-a ® gave the diol 16a (77% ee). This was purified via the crystalline bis-3,5-dinitrobenzoate 16b to give pure 16a (99% ee), which furnished (1S,5R,7S)-17 by acid treatment.…”

Section: Synthesis Of (2)-exo-and (2)-endo-isobrevicominsmentioning

confidence: 99%

Pheromones: synthesis and bioactivity

Mori¹

1997

Chem. Commun.

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Pheromones play an important role in chemical communication among organisms. Various chiral and non-racemic pheromones have been identified since the late 1960s. Their enantioselective syntheses were achieved so as to establish the absolute configuration of the naturally occurring pheromones and also to clarify the relationship between absolute configuration and the bioactivity of the chiral pheromones. Four recent examples of pheromone synthesis are given. The enantiomers of sordidin 14, the banana weevil pheromone, have been synthesized starting from (S)-propylene oxide. (2)-exo-Isobrevicomin 17 and its (2)-endo-isomer 21, the components of the volatiles of the mountain pine beetle, have been synthesized by employing the Sharpless asymmetric dihydroxylation and lipase-catalysed acetylation as the key reactions. The enantiomers of (Z)-hexadeca-7,15-dien-4-olide 24, the sex pheromone of the yellowish elongate chafer, have been synthesized via lipase-catalysed resolution. Lurlene 27, the pheromone of the green flagellate Chlamydomonas allensworthii, has been synthesized by employing a phenyl sulfone coupling reaction as the key reaction.The relationships between absolute configuration and bioactivity are diverse. For example, neither the (R)-nor the (S)-enantiomer of sulcatol 10, the aggregation pheromone of the ambrosia beetle Gnathotrichus sulcatus, is bioactive, but when combined to give an enantiomeric mixture they become active. In the case of olean 46, the olive fruit fly pheromone, (R)-46 is active for the males, while (S)-46 is active for the females.

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Section: Synthesis Of (2)-exo-and (2)-endo-isobrevicominsmentioning

confidence: 99%

Pheromones: synthesis and bioactivity

Mori¹

1997

Chem. Commun.

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“…13, No. 2, 2002 bonds of 9 and 10, mediated by the commercially available Sharpless reagents (AD-mix-a â and AD-mix-b â ), 12 which have already been used to synthesize the (-)-exoisobrevicomin (1), 3,4 (+)-exo-brevicomin (2) and respective endo isomer 13 , furnished the corresponding diols 11 and 12, in 76-80% yield. Since compounds 9 and 10 were also primary halides, the dihydroxylation reaction was carried out under buffered conditions by the addition of NaHCO 3 in order to avoid the formation of an epoxy intermediate.…”

Section: Resultsmentioning

confidence: 99%

“…1 The isolation and the first synthesis of (-)-exoisobrevicomin (1), (1S,5R,7S)-5-ethyl-7-methyl-6,8-dioxabicyclo[3.2.1]octane, and the respective hydroxylated derivatives were reported by Francke and co-workers 2 in 1996. Further alternative strategies for the preparation of this compound were reported by Mori and co-workers 3 in 1997, and by Taniguchi and co-workers 4 in 1998. Compound 1 is a new naturally occurring isomer of (+)-exobrevicomin (2), with opposite absolute configuration at the stereogenic centers, produced by males of the beetles Dendroctonus ponderosae.…”

Section: Introductionmentioning

confidence: 99%

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Asymmetric Synthesis of exo-Isobrevicomin and exo-Brevicomin via Conjugated Addition of Primary Alkyl Iodides to alpha,beta-Unsaturated Ketones

Sousa¹,

Resck²

2002

J. Braz. Chem. Soc.

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(-)-exo-Isobrevicomina (1) e (+)-exo-brevicomina (2) são substâncias voláteis produzidas pelos besouros machos Dendroctonus ponderosae, os quais habitam árvores do gênero Pinus encontradas no hemisfério norte, freqüentemente causando a morte dos hospedeiros. Objetivando a obtenção desses feromônios de agregação, que apresentam a estrutura 6,8-dioxabiciclo[3.2.1]octano, as estratégias sintéticas utilizadas nesse trabalho tiveram como etapas-chaves a di-hidroxilação assimétrica de Sharpless e a adição conjugada, promovida pela liga Zn(Cu) em meio aquoso e acelerada por ultra-som. A adição conjugada dos acetonídeos 13 e 14 às respectivas cetonas insaturadas (metilvinil-cetona e etil-vinil-cetona) gerou os adutos 15 e 16. A ciclização intramolecular catalisada dos compostos 15 e 16 com ácido fosfotungstico (H 3 PW 12 O 40 ) forneceu a exo-isobrevicomina (1) e a exo-brevicomina (2).(-)-exo-Isobrevicomin (1) and (+)-exo-brevicomin (2) are volatile substances produced by males of the beetles Dendroctonus ponderosae, which inhabit pine trees found in the northern hemisphere, frequently causing the death of their host. In order to obtain these aggregation pheromones, which present the 6,8-dioxabicyclo[3.2.1]octane structure, the synthetic strategies utilized in this work had as key steps the Sharpless asymmetric dihydroxylation and the conjugated addition, promoted by the Zn(Cu) couple in aqueous medium and accelerated by ultrasound. The conjugated addition of acetonides 13 and 14 to the respective unsaturated ketones (methyl vinyl ketone and ethyl vinyl ketone) furnished the adducts 15 and 16. The intramolecular catalyzed cyclization of compounds 15 and 16 with phosphotungstic acid (H 3 PW 12 O 40 ) produced exo-isobrevicomin (1) and exo-brevicomin (2).

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“…In this vein, Mori et al [25] reported an efficient and highly enantioselective chemoenzymatic synthesis of both the exo-and endo-isomers of isobrevicomin (11), which had been isolated by Francke et al [26] in 1996 as components of the volatiles obtained from male mountain pine beetles (Dendroctonus ponderosae). The enzymatic step was a lipase-catalyzed asymmetric acetylation with vinyl acetate and immobilized lipase PS (Amano).…”

Section: Synthesis Of Bicyclic Ketal Phero-monesmentioning

confidence: 99%

Biocatalysis Applied to the Synthesis of Pheromones

Aleu¹,

Bustillo²,

Hernández-Galán³

et al. 2007

COC

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The application of biologically derived catalysts to the synthesis of agrochemicals has become increasingly popular in recent years. In most cases, the aim of using a biotransformation is either to introduce chirality into the molecule, to achieve a regioselective functionalization, or to selectively convert a functional group among other groups with similar reactivity. Pheromones, which have recently been commercialized as agrochemicals, are generally used in enantiopure forms with their intentional mixtures. Since they are usually highly effective, only very small quantities are needed to achieve the desired activity. This review, with approximately 200 references covering the period previous to December 2004, describes various efficient means of preparing optically pure pheromones and their precursors with the aid of isolated enzymes and microorganisms serving as catalysts.

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Pheromone Synthesis, CLXXVIII. – Synthesis of (−)‐exo‐Isobrevicomin and Its (−)‐endo Isomer, the Components of The Male‐Produced Volatiles of the Mountain Pine Beetle, Dendroctonus ponderosae

Cited by 16 publications

References 7 publications

Pheromones: synthesis and bioactivity

Pheromones: synthesis and bioactivity

Asymmetric Synthesis of exo-Isobrevicomin and exo-Brevicomin via Conjugated Addition of Primary Alkyl Iodides to alpha,beta-Unsaturated Ketones

Biocatalysis Applied to the Synthesis of Pheromones

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