Synthesis of All the Stereoisomers of 10,14‐Dimethyloctadec‐1‐ene, 5,9‐Dimethyloctadecane and 5,9‐Dimethylheptadecane, the Sex Pheromone Components of the Apple Leafminer,
            <i>Lyonetia</i>
            <i>prunifoliella</i>

Tamagawa, Hideki; Takikawa, Hirosato; Mori, Kenji

doi:10.1002/(sici)1099-0690(199905)1999:5<973::aid-ejoc973>3.0.co;2-#

Cited by 16 publications

(9 citation statements)

References 9 publications

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“…Its hydrolysis gave the key hydroxyacid 11, which was cyclized under standard conditions into the desired pheromone 12. An analogous approach with isomerization of the double bond of another monoterpenoid, nerol (45), was used to prepare of 3,7-dimethyl-2Z,7-octadien-1-ol propionate (48), a component of the California red scale (A. aurantii) pheromone [25,26]. Here the double bond in the terminal position was substituted by treatment of epoxyester 46 with t-butylhypochlorite, which produced allyl alcohol 47, deoxygenation of which gave the required 48.…”

Section: Monoterpenoids Functionalized By Epoxidationmentioning

confidence: 99%

“…It has also been widely used to synthesize insect pheromones [43][44][45][46][47][48][49][50][51][52][53][54] and is a convenient and practical method for preparing O-containing compounds.…”

Section: Ozonolysismentioning

confidence: 99%

“…A synthesis of all stereoisomers of 10,14-dimethyloctadec-1-ene (152a-d), 5,9-dimethyloctadecane (153a-d), and 5, 9- dimethylheptadecane (40a, 41a, and 155a,b), components of the apple leafminer (Lyonetia prunifoliella) sex pheromone, was proposed starting with citronellol enantiomers (30) and methyl 2-methyl-3-hydroxybutanoate (149) [45]. Required isomers of 148 were prepared from (R)-and (S)-citronellol (30), which was first converted to acetoxyalcohol 146 [46] and then alkylated through the corresponding tosylate [47].…”

Section: Ozonolysismentioning

confidence: 99%

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Insect Pheromones Synthesized by Oxidative Transformations of Natural Monoterpenoids

et al. 2005

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The literature on oxidative transformations of natural monoterpenoids to synthesize insect pheromones was reviewed.The literature on pheromone chemistry is broad and reflects the consistent interest in this area over the last 20 years in the form of monographs [1-7] and reviews [8][9][10][11][12][13][14][15].Insect pheromones known today are rather simple molecules (less than four asymmetric centers and four functional groups). Therefore, the "ideal" substrate (chiral or achiral) for most such structures is a moderately functionalized molecule, in particular, hydroxy-and amino-acids in addition to monoterpenoids. The last class of compounds is the most accessible for this series and is especially convenient for the synthesis of molecules with a branched C skeleton, primarily isoprenoid pheromones.Oxidative methods of transforming monoterpenoids are the most convenient and widely used methods for carrying out various transformations of starting molecules and introducing most known functional groups. Considering this aspect, articles on the synthesis of insect pheromones that for one reason or another did not appear in previous reviews are reviewed herein. ALLYLIC OXIDATION BY SELENIUM DIOXIDEOne of the most common methods for functionalizing the C skeleton of unsaturated monoterpenoids containing an isopropylidene group is regio-and stereoselective oxidation at the allylic position, for example, by SeO 2 , of geraniol (1) and its derivatives or similar compounds. This method enables introduction into molecules of hydroxy-or oxo-functions that can be used in further transformations.For example, treatment of geranylacetate (2) with a stoichiometric or catalytic (with t-BuOOH) amount of SeO 2 followed by hydride reduction gives unsaturated hydroxyacetate 3, which is widely used to synthesize insect pheromones [16][17][18][19].In particular, 3 was oxidized to aldehyde 4, which was then converted to the olefin by n-propylidenephosphorane [16], to prepare racemic 5,9-dimethylheptadecane (7), the sex pheromone of the pear leaf blister moth (Leucoptera scitella Zeller). Organocuprate coupling of the resulting allylic acetate 5 with n-hexylmagnesium bromide led to 5,9-dimethyl-3,5,9-heptadecatriene (6), exhaustive hydrogenation of which gave the desired pheromone 7.Condensation of bromoacetate 8 wth sodium malonic ester was used [17] to synthesize 10-hydroxy-4,8-dimethyl-4E,8E-decadienoic acid (11), an acyclic precursor of ferrulactone I (12), which is the principal component of the aggregation pheromone of the rusty grain beetle (Cryptolestes ferrugineus Stephen). Decarboxylation of the resulting triester 9 and subsequent saponification gave the key hydroxyacid 11, lactonization of which by bis-(4-t-butyl-N-isopropylimidazol-2-yl)disulfide gave the desired 12.

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Section: Monoterpenoids Functionalized By Epoxidationmentioning

confidence: 99%

Section: Ozonolysismentioning

confidence: 99%

Section: Ozonolysismentioning

confidence: 99%

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Insect Pheromones Synthesized by Oxidative Transformations of Natural Monoterpenoids

et al. 2005

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“…The chiral 1,5-dimethylalkane subunit is ubiquitous among many biologically active natural products (Figure 1), such as vitamins, 1,2 phytol, 3 insect pheromones [4][5][6][7][8][9][10][11][12] , marine natural M A N U S C R I P T A C C E P T E D ACCEPTED MANUSCRIPT products, 13,14 archaeal lipids, [15][16][17][18] and the bacterial membrane lipids (β-D-mannosyl phosphomycoketides). 19,20 Total synthesis of these methyl-branched natural products has been an interesting and active subject for several decades due to their structural determinations and their increasing biological and biomedical applications.…”

Section: Introductionmentioning

confidence: 99%

“…We also prepared four stereopure 1,5-dimethylalkane C 10 chirons ( Figure 2C) from (S)-1 and/or (R)-1. To further evaluate the synthetic value of these chirons in natural product synthesis, we prepared the vitamin E C 14 (3R, 7R, 11R) VII: 15,16 Archaeol lipid, a lipid isolated from Methanobacterium thermoautotrophicum III: [4][5][6][7][8] Insect pheromone…”

Section: Introductionmentioning

confidence: 99%

Synthesis of stereopure acyclic 1,5-dimethylalkane chirons: building blocks of highly methyl-branched natural products

Piccirilli

2013

Tetrahedron

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Synthesis of the Enantiomers ofanti-2,6-Dimethylheptane-1,7-diol Monotetrahydropyranyl Ether and Their Conversion into the Enantiomers of the Sex Pheromone Components of the Apple Leafminer,Lyonetia prunifoliella

Nakamura¹,

Mori

2000

Eur. J. Org. Chem.

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Synthesis of All the Stereoisomers of 10,14‐Dimethyloctadec‐1‐ene, 5,9‐Dimethyloctadecane and 5,9‐Dimethylheptadecane, the Sex Pheromone Components of the Apple Leafminer, Lyonetia prunifoliella

Cited by 16 publications

References 9 publications

Insect Pheromones Synthesized by Oxidative Transformations of Natural Monoterpenoids

Insect Pheromones Synthesized by Oxidative Transformations of Natural Monoterpenoids

Synthesis of stereopure acyclic 1,5-dimethylalkane chirons: building blocks of highly methyl-branched natural products

Synthesis of the Enantiomers ofanti-2,6-Dimethylheptane-1,7-diol Monotetrahydropyranyl Ether and Their Conversion into the Enantiomers of the Sex Pheromone Components of the Apple Leafminer,Lyonetia prunifoliella

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