- SYNTHESIS OF Z-OLEFIN-CONTAINING LEPIDOPTERAN INSECT PHEROMONES
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The present invention is directed to methods of synthesizing insect pheromones, particularly lepidopteran insect pheromones, their precursors and derivatives from inexpensive, readily available starting materials using olefin metathesis catalysis.
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Paragraph 0212; 0213
(2013/09/12)
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- Concise syntheses of insect pheromones using Z-Selective cross metathesis
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Very short synthetic routes to nine cisolefin-containing pheromones containing a variety of functionality, including an unconjugated (E,Z) diene, are reported (see scheme). These lepidopteran pheromones are used extensively for pest control, and were easily prepared using ruthenium-based Z-selective cross metathesis, highlighting the advantages of this method over less efficient ways to form Z olefins.
- Herbert, Myles B.,Marx, Vanessa M.,Pederson, Richard L.,Grubbs, Robert H.
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p. 310 - 314
(2013/02/23)
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- New synthesis of (±)-cis-disparlure, pheromone of female gypsy moth (Porthetria dispar) species
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(±)-cis-Disparlure was synthesized in an overall yield of 50% via stereoselective addition of isoheptylmagnesium bromide to α-bromododecanal.
- Kel'in,Kulinkovich
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p. 1446 - 1448
(2007/10/03)
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- A highly stereoselective preparation of syn-1,2-diols from secondary α-allenic alcohols via iodocyclization. Synthesis of (±)-threo-L-factor and (±)-disparlure
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The iodocyclization of the N-tosyl carbamates 5 of secondary α-allenic alcohols 4 is described. The reaction sequence involves the addition of iodine to the terminal olefin of the allene moiety of 5 resulting in the formation of an isomeric mixture of Z and E diiodides 6 and 7. This initial process is followed, in the same pot, by reaction of the diiodides with silver carbonate. Hydrolysis of the resulting trans imino carbonates 8 provides syn-1,2-diols 10 in highly diastereoselective (>50:1) and regioselective (>20:1) fashion. Oxazolidinones 9 are minor products that arise from the participation of the carbamate nitrogen atom in the cyclization reaction. The regioselectivity of the cyclization reaction from 6/7 to 8 is highly dependent upon the reaction solvent with the optimum results being obtained in ether/MeCN mixtures (10:1 to 50:1) or CH2Cl2. The synthetic utility of the vinyl iodo diols 10 is demonstrated by the synthesis of (±)-threo-5-hydroxy-4-decanolide (17) ((±)-threo-L-factor) and (±)-cis-7,8-epoxy-2-methyloctadecane (24) ((±)-disparlure). The key step in each synthesis involves the conversion of the vinyl iodide moiety of 10 into the alkynes 15 or 18 (from 10j and 10k, respectively) via a high-yielding dehydrohalogenation reaction.
- Friesen,Giroux
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p. 1857 - 1865
(2007/10/02)
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- Tritium-Labeled Enantiomers of Disparlure. Synthesis and in Vitro Metabolism
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Both of the enantiomers of disparlure, the gypsy moth sex attractant, have been prepared at high specific activity (58 Ci/mmol) by homogeneous tritiation of the optically active alkenyl oxiranes.An improved preparation of the racemic disparlure is also described.The radiolabeled epoxides are cleanly converted to a single product by enzymes isolated from adult gypsy moths (Lymantria dispar).Enzymatic activity obtained from male antennae showed the highest conversion; enzymes isolated from female antennae and from male and female legs showed lower activity.The identification of the metabolite as the threo-7,8-diol is established by independent synthesis and by chemical derivatizations to the diacetate, n-butylboronate, and bis(trimethylsilyl) ether.A symmetrical epoxide analogous to disparlure is converted to a diol product at a significantly lower rate.
- Prestwich, Glenn D.,Graham, Steven McG.,Kuo, Jing-Wen,Vogt, Richard G.
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p. 636 - 642
(2011/07/06)
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- A NEW VARIANT OF THE SYNTHESIS OF DISPARLURE VIA ACETYLENIC INTERMEDIATES
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Disparlure, the sexual feromone of the Gypsy Moth, has been prepared via the known intermediate 2-methyl-7-octadecyne, using a new constructional principle: C9+C10->C19.The so far undescribed 7-methyl-1-octyne was used as the C9 component.The advantages of this procedure consist in higher yields of disparlure and in a substantial simplification of the method of purification of 2-methyl-7-octadecyne.
- Jonas, Jaroslav,Slanina, Pavel,Humpa, Otakar,Mazal, Ctibor
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p. 857 - 859
(2007/10/02)
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- SILICON IN ORGANIC SYNTHESIS. STREREOSELECTIVE SYNTHESIS OF SOME INSECT SEX PHEROMONES
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Trialkylsilallyl anion is alkylated by alkyl halides to give regio- and strereo-selectively the γ-product with trans-strereochemistry at double bond.The trans-vinylsilanes are transformed strereoselectively to Z-vinyl iodides.Coupling of the vinyl idiodes with organometallic reagents gives Z-alkenes.This approach has been applied to the synthesis of several insect sex pheromones.
- Chan, T. H.,Koumaglo, K.
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p. 109 - 120
(2007/10/02)
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- A New Synthesis of (Z)-7,8-Epoxy-2-methyloctadecane (Disparlure)
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Alkylation of the dianion of propargyl alcohol with 1-bromodecane in Li/liq.NH3 affords tridec-2-yn-1-ol (II) which on hydrogenation in the presence of Lindlar's catalyst yields tridec-2Z-en-1-ol (III).Treatment of III with MsCl/Et3N in anhyd.CH2Cl2 at low temperature gives the mesylate (IV) which undergoes smooth coupling reaction with 1-bromo-4-methylpentane (V) to produce 2-methyloctadec-7Z-ene (VI).Reactions of VI with m-chloroperbenzoic acid in anhyd.CH2Cl2 furnishes the title compound (I).
- Vig, O. P.,Sharma, M. L.,Kumari, Sarla,Vohra, Neelam
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p. 860 - 861
(2007/10/02)
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- REGIOSELECTION IN THE ALKYLATION OF TRIMETHYLSILYLALLYL ANION- STEREOSELECTIVE SYNTHESIS OF DISUBSTITUTED ALKENES.
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The regioselection in the alkylation of trimethylsilylallyl anion can be controlled by the use of Schlosser's base to give predominately γ-product with trans geometry at the double bond.Application of this approach to the synthesis of Z-9-tricosene and the Gypsy month sex pheromone is demonstrated.
- Koumaglo, K.,Chan, T. H.
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p. 717 - 720
(2007/10/02)
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- Preparation of (Z)-Alkenes, Ketones, and Alkynes via Trialkyltin Chloride Induced Intramolecular Transfer Reaction of Lithium 1-Alkynyltrialkylborates. Stereoselective Synthesis of the Sex Pheromones of the Douglas Fir Tussock Moth, the Gipsy Moth, and the Wild Silkmoth Antheraea poly...
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Trialkyltin chloride was used to induce selective migration of a primary alkyl group from the boron atom to the adjacent acetylenic carbon atom of lithium 1-alkynyltrialkylborate complexes derived from B-alkyl-9-borabicyclononanes and 1-lithio-1-alkynes.Protonolysis of the resultant olefinic intermediate substituted with boron and tin functionalities on the adjacent vinyl carbon atoms provided the corresponding (Z)-alkene.Oxidation or iodination afforded the corresponding ketone or alkyne, respectively.The high selectivity of 9-borabicyclononane as ahydroborating agent toward the terminal double bond allowed easy incorporation of internal double bond and triple bond into the alkyl group of the starting B-alkyl-9-borabicyclononane.Various types of diene, enyne, enone, ynone and diyne were synthesized.These reactions were also successfully adopted for the stereoselective synthesis of sex pheromones of the Douglas fir tussock moth, the gypsy moth, and the wild silkmoth Antheraea polyphemus.
- Wang, Kung K.,Chu, Kai-Hsuan
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p. 5175 - 5178
(2007/10/02)
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- Olefin Inversion. 3. Preparations and Reductions of vic-Halohydrin Trifluoroacetates
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Treatment of alkenes with N-bromo- and N-chlorosuccinimide in trifluoroacetic acid resulted in stereospecific anti addition of the elements of trifluoroacetyl hypobromite and hypochlorite, respectively.Heating the vic-bromo- or -chlorohydrin trifluoroacetates with NaI in DMF produced olefins with inversion of geometry.Treatment of the adducts with Zn in DMF reduced them to olefins with retention of geometry.Reductive transformations involving the chlorohydrin trifluoroacetates were virtually stereospecific, whereas those involving the bromohydrin trifluoroacetates were >90percent stereoselective for NaI reductions and only 60-90percent stereoselective for reductions by Zn.
- Sonnet, Philip E.
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p. 154 - 157
(2007/10/02)
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