- Novel Enantioselective Syntheses of Optically Active (1R)-cis- and (1R)-trans-Chrysanthemic Acids.
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Dimethyl dimedone, a non chiral and cheap compound, has been converted to the optically actives 1-(R)-cis- and 1-(R)-trans-chrysanthemic acids possessing high economic value.These processes involve as the key steps (i) a cyclopropanation reaction (ii) a Grob fragmentation and (iii) a lipase monitored hydrolysis of a prochiral diacetate.
- Krief, Alain,Surleraux, Dominique,Ropson, Nathalie
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- Total Syntheses of All Six Chiral Natural Pyrethrins: Accurate Determination of the Physical Properties, Their Insecticidal Activities, and Evaluation of Synthetic Methods
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Chiral total syntheses of all six insecticidal natural pyrethrins (three pyrethrin I and three pyrethrin II compounds) contained in the chrysanthemum (pyrethrum) flower were performed. Three common alcohol components [(S)-cinerolone, (S)-jasmololone, and (S)-pyrethrolone] were synthesized: (i) straightforward Sonogashira-type cross-couplings using available (S)-4-hydroxy-3-methyl-2-(2-propynyl)cyclopent-2-en-1-ones (the prallethrin alcohol) for (S)-cinerolone (overall 52% yield, 98% ee) and (S)-pyrethrolone (overall 54% yield, 98% ee) and (ii) traditional decarboxylative-aldol condensation and lipase-catalyzed optical resolution for (S)-jasmololone (overall 16% yield, 96% ee). Two counter acid segments [(1R,3R)-chrysanthemic acid (A) and (1R,3R)-second chrysanthemic acid precursor (B)] were prepared: (i) C(1) epimerization of ethyl (±)-chrysanthemates and optical resolution using (S)-naphthylethylamine to afford A (96% ee) and (ii) concise derivatization of A to B (96% ee). All six pyrethrin esters (cinerin I/II, jasmolin I/II, and pyrethrin I/II) were successfully synthesized utilizing an accessible esterification reagent (TsCl/N-methylimidazole). To investigate the stereostructure-activity relationship, all four chiral stereoisomers of cinerin I were synthesized. Three alternative syntheses of (±)-jasmololone were investigated (methods utilizing Piancatelli rearrangement, furan transformation, and 1-nitropropene transformation). Insecticidal activity assay (KD50 and IC50) against the common mosquito (Culex pipiens pallens) revealed that (i) pyrethrin I > pyrethrin II, (ii) pyrethrin I (II) > cinerin I (II) ? jasmolin I (II), and (iii) "natural" cinerin I ? three "unnatural" cinerin I compounds (apparent chiral discrimination).
- Ashida, Yuichiro,Kawamoto, Momoyo,Matsuo, Noritada,Moriyama, Mizuki,Tanabe, Yoo
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p. 2984 - 2999
(2020/03/24)
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- Cyclopropanation of Terminal Alkenes through Sequential Atom-Transfer Radical Addition/1,3-Elimination
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An operationally simple method to affect an atom-transfer radical addition of commercially available ICH2Bpin to terminal alkenes has been developed. The intermediate iodide can be transformed in a one-pot process into the corresponding cyclopropane upon treatment with a fluoride source. This method is highly selective for the cyclopropanation of unactivated terminal alkenes over non-terminal alkenes and electron-deficient alkenes. Due to the mildness of the procedure, a wide range of functional groups such as esters, amides, alcohols, ketones, and vinylic cyclopropanes are well tolerated.
- Tappin, Nicholas D. C.,Michalska, Weronika,Rohrbach, Simon,Renaud, Philippe
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supporting information
p. 14240 - 14244
(2019/08/26)
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- Method for preparing chiral trans-chrysanthemic acid
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The invention provides a method for preparing chiral trans-chrysanthemic acid, belongs to the field of organic synthesis, and relates to a method for synthesis of chiral ethyl chrysanthemumate from 2,5-dimethyl-2,4-hexadiene and ethyl diazoacetate by an asymmetric cyclopropanation reaction and for hydrolysis to form chiral chrysanthemic acid. A chiral copper catalyst adopted is prepared in situ from a copper salt and a chiral tridentate P,N,N-ligand in various polar and non-polar solvents. The chiral trans-chrysanthemic acid can be conveniently synthesized, and the percentage of enantiomeric excess is as high as 95%. The method has the characteristics such as simple operation, easy availability of raw materials, wide application range of substrates and high enantioselectivity.
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Paragraph 0045-0050; 0084-0087; 0092-0095
(2019/10/29)
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- Syntheses of racemic and scalemic cis-chrysanthemic acid from β,γ-unsaturated cyclohexanol
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2,2,5,5-Tetramethylcyclohexane-1,3-dione is a valuable starting-material precursor of cis-chrysanthemic acid. The (1S)-stereoisomer is a precursor of pyrethrin I, the most active natural insecticide from Chrysanthemum cinerariifolium, whereas the (1R)-stereoisomer is efficiently transformed to deltamethrin, the most active commercially available pyrethroid insecticide. Several intermediates have been identified and used with variable success for that purpose.
- Krief, Alain,Jeanmart, Stéphane,Gondal, Humaira Y.,Kremer, Adrian
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p. 2123 - 2167
(2013/02/23)
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- An enantiospecific route to (+)-(1R,3S)-cis-chrysanthemic acid from (-)-d-pantolactone
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In this paper, a novel route for the synthesis of (+)-(1R,3S)-cis- chrysanthemic acid is described. The use of readily available (-)-d-pantolactone as a starting point, application of ring-closing metathesis to form the cyclopentene intermediate, and Haller-Bauer/Grob-type fragmentation to form the target compound are the highlights of the present synthesis. Georg Thieme Verlag Stuttgart.
- Hajare, Atul K.,Datrange, Laxmikant S.,Murthy,Bhuniya, Debnath,Reddy, D. Srinivasa
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experimental part
p. 1067 - 1070
(2011/06/19)
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- Unprecedented dual reactivity of anhydrous potassium hydroxide in cascade cyclopropannelation/Haller-Bauer-scission/Grob-fragmentation reactions
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We report an unprecedented type of reactivity of 'anhydrous potassium hydroxide' ('APH') in which it plays, over a large variety of related educts, sequentially the role of base and nucleophile. Some insight into the structure of reactive species as well as comparative reactivity of related reagents prepared by fusion of commercially available potassium hydroxide or by adding stoichiometric amount of water to potassium hydride is provided.
- Krief, Alain,Kremer, Adrian
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body text
p. 4306 - 4309
(2010/09/20)
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- A practical method for O-acylation of N -hydroxythiazole-2(3 H)-thiones
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O-Acylation of 4- and 4,5-substituted N-hydroxythiazole-2(3H)-thiones occurred in solutions of acetone upon treatment with solid K2CO3 and a variety of neat acyl chlorides (primary, secondary, and tertiary alkyl, aryl; 60-87% yield; ~10 g scale).
- Schur, Christine,Gross, Andreas,Hartung, Jens
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experimental part
p. 538 - 542
(2010/06/13)
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- Novel synthesis of (d,l)-cis-chrysanthemic acid involving α,α′-dibromination of 2,2,5,5-tetramethylcyclohexane-1,3-dione: application to the enantioselective synthesis of (1R)-cis-chrysanthemic acid
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cis-Chrysanthemic acid has been prepared in a few steps from dimethyldimedone via dibromination at alpha positions of each carbonyl carbons. The trans-dibromide which is almost exclusively formed has been isomerized to its cis-stereoisomer by highly chemoselective tandem H/K-K/H exchanges involving potassium bases at low temperature (-40 °C). Carbocyclization of the potassium enolate intermediate takes place at around -30 °C and provide the bicyclo[3.1.0]-hexane skeleton. Lithiated bases behave differently and mainly lead to Br/M rather than to H/M exchange. We have been unsuccessful in using state of the art enantioselective metallation reactions to achieve the enantioselective synthesis of (1R)-cis-chrysanthemic acid using the disclosed strategy. This therefore still remains challenge.
- Krief, Alain,Dumont, Willy,Kremer, Adrian
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scheme or table
p. 2398 - 2401
(2009/07/26)
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- Diastereoselective bromination of compounds bearing a cyclohex-3-enol moiety: Application to the enantioselective synthesis of (1R)-cis-deltamethrinic acid
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(Chemical Equation Presented) (1R)-cis-Chrysanthemic acid has been prepared in a few steps with complete control of the relative and absolute stereochemistry. Some mechanistic aspect of the addition of bromine to the C,C double bond of 2,2,5,5-tetramethylcyclohex-3-enol is disclosed.
- Krief, Alain,Jeanmart, Stephane,Kremer, Adrian
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experimental part
p. 9795 - 9797
(2009/04/07)
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- Diastereoselective epoxidation of compound bearing a cyclohex-3-enol moiety: Application to the enantioselective synthesis of (1R)-trans-chrysanthemic acid and (1R)-cis-deltametrinic acid
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We disclose the synthesis of enantiomeric (1S)-cis- and (1R)-cis-chrysanthemic acids precursors of S-bioallethrin and deltamethrin the most active indoor and outdoor insecticides respectively. It involves an original strategy which takes advantage of the complete stereocontrolled epoxidation of an homoallylalcohol and the synthesis in the same pot of precursors of each of the two enantiomers of cis-chrysanthemic acid, bearing functional groups possessing similar reactivity but having different structural behavior which allow their easy separation.
- Krief, Alain,Jeanmart, Stephane,Kremer, Adrian
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scheme or table
p. 1075 - 1079
(2009/06/28)
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- Fragmentation of 4-sulfonylbicyclo[3.1.0]hexan-2-ones as the key step in the enantioselective synthesis of (1R)-cis-chrysanthemic acid involving desymmetrization of 3,3,6,6-tetramethylbicyclo[3.1.0]hexane-2,4-dione
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t-BuOK-H2O (7.6:2.3) in THF or DMSO allows the efficient Grob-type fragmentation of 4-sulfonyl-bicyclo[3.1.0]hexan-2-ones which cannot be achieved by potassium hydroxide in DMSO as we originally described. Georg Thieme Verlag Stuttgart.
- Krief, Alain,Kremer, Adrian
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p. 607 - 610
(2007/10/03)
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- Practical copper-catalyzed asymmetric synthesis of chiral chrysanthemic acid esters
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Practical copper salicylaldimine complex catalysts have been developed for the asymmetric synthesis of chiral chrysanthemic acid esters by the cyclopropanation reaction of 2,5-dimethyl-2,4-hexadiene with tert-butyl diazoacetate. First, the effects of the substituents on the salicylaldehyde moiety in the copper salicylaldimine complex (copper Schiff base complex) on the catalytic activity and the stereoselectivities were investigated. As a result, a substitution of hydrogen at the 5-position with the nitro group on the salicylaldehyde moiety was found to enhance the catalytic efficiency. In addtition, a combination catalyst of the copper Schiff base complex with Lewis acid was found to also enhance the catalytic efficiency and achieved 90% chemical yield and 91% ee at 20 °C with 0.1 mol % catalyst loading. Furthermore, the asymmetric induction mechanism of the cyclopropanation reaction catalyzed by the copper Schiff base complex was studied using density functional calculations.
- Itagaki, Makoto,Suenobu, Katsuhiro
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p. 509 - 518
(2012/12/31)
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- Nitrile biotransformation for highly enantioselective synthesis of 3-substituted 2,2-dimethylcyclopropanecarboxylic acids and amides
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Biotransformations of differently configured 2,2-dimethyl-3-substitued-cyclopropanecarbonitriles were studied using a nitrile hydratase/amidase-containing Rhodococcus sp. AJ270 whole-cell catalyst under very mild conditions. Although all of the cis-3-aryl-2,2-dimethylcyclopropanecarbonitriles appeared inert toward the biocatalyst, a number of racemic trans-isomers efficiently underwent a highly enantioselective hydrolysis to produce (+)-(1R,3R)-3-aryl-2,2-dimethylcyclopropanecarboxylic acids and (-)-(1S,3S)-3-aryl-2,2-dimethylcyclopropanecarboxamides in high yields with excellent enantiomeric excesses in most cases. The overall enantioselectivity of the biotransformations of nitriles originated from the combined effects of 1R-enantioselective nitrile hydratase and amidase, with the later being a dominant factor. The influence of the substrates on both reaction efficiency and enantioselectivity was discussed in terms of steric and electronic effects. Coupled with chemical transformations, biotransformations of nitriles provided convenient syntheses of optically pure geminally dimethyl-substituted cyclopropanecarboxylic acids and amides, including chrysanthemic acids, in both enantiomeric forms.
- Wang, Mei-Xiang,Feng, Guo-Qiang
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p. 621 - 624
(2007/10/03)
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- Enzyme catalysed kinetic resolution of racemic 2,2-dimethyl-3-(2,2- disubstituted vinyl) cyclopropane carboxylic acids anchored on polymer supports
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Kinetic resolution of trans-substituted cyclopropane carboxylic acids anchored on a solid support by lipase is described.
- Nanda,Bhaskar Rao,Yadav
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p. 5905 - 5908
(2007/10/03)
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- Novel synthesis of vinyl cyclopropane carboxylic acids: Application to the synthesis of (d,l)- and (d)-cis-chrysanthemic acid
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Reaction of sulfur ylides with suitably 4-functionalized-5,5-dimethyl-2-cyclopentenones allows an efficient entry to the bicyclo[3.1.0]hexan-2-one skeleton which proved to be a valuable precursor of vinyl cyclopropane carboxylic acids. Application to the synthesis of (d,l)- and (d)-(cis)-chrysanthemic acid is described.
- Krief, Alain,Swinnen, Dominique
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p. 7123 - 7126
(2007/10/03)
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- Electron transfer photochemistry of chrysanthemol: An intramolecular S(N)2' reaction of a vinylcyclopropane radical cation
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The electron transfer photochemistry of optically pure (1R,3S)-(+)-cis-chrysanthemol (cis-2) results in the formation of (R)-5-(1-(p-cyanophenyl)-1-methylethyl)-2,2-dimethyl oxacyclohex-3-ene (4) with significant retention of optical activity. The product is rationalized via nucleophilic attack of the alcoholic function of the radical cation on the terminal carbon of the vinyl group with simultaneous replacement of an isopropyl radical as an intramolecular leaving group in an apparent S(N)2' reaction. This mode of attack is unprecedented in vinylcyclopropane radical cations and is interpreted as evidence for the significant role that relief of ring strain and its avoidance play in determining the course of nucleophilic capture in radical cationic systems.
- Herbertz, Torsten,Roth, Heinz D.
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p. 10954 - 10962
(2007/10/03)
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- Molecular chiral recognition in supercritical solvents
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The intensity of molecular chiral interactions resulting in differences between physical and chemical properties of diastereomeric molecules is solvent dependent. This difference makes it possible to separate the enantiomers of a given substance by using chiral agents. A solvent of suprcritical state was involved to study its influence on molecular chiral recognition. It was observed that the differences between the diastereomers in supercritical CO2 are so big compared to traditional solvents that a novel, more efficient method for optical resolution can be developed, employing a variety of resolution agents in a much wider range than it was previously assumed.
- Fogassy, Elemer,Acs, Maria,Szili, Timea,Simandi, Bela,Sawinsky, Janos
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p. 257 - 260
(2007/10/02)
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- Lipase catalysed kinetic resolution of racemic (±)2,2-dimethyl-3-(2-methyl-1-propenyl)-cyclopropane carboxyl esters
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Optically active (1R)(-) and (1S)(+)-trans-Chrysanthemic acid and its esters were prepared from corresponding racemic methyl ester by lipase mediated enantioselective hydrolysis, is described.
- Bhaskar Rao,Rehman,Krishnakumari,Yadav
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p. 2611 - 2614
(2007/10/02)
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- Asymmetric Copper-Catalyzed Cyclopropanation of Trisubstituted and Unsymmetrical cis-1,2-Disubstituted Olefins: Modified Bis-Oxazoline Ligands
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The Cu(I) complexes of new bis-oxazolines (3-7) prepared from the corresponding amino alcohols and malono-bis-imidate exhibit high enantioselectivity of up to 94 percent ee in the catalytic cyclopropanation of trisubstituted and unsymmetrical cis-1,2-disubstituted olefins.New diazoacetate reagents have also been developed giving high trans/cis ratios of up to 99:1 trans.
- Lowenthal, Richard E.,Masamune, Satoru
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p. 7373 - 7376
(2007/10/02)
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- From Δ3-carene to the most biologically active insecticides: A convenient and efficient synthesis of (+)-(1R)-cis-chrysanthemic acid
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A convenient and economical synthesis of (+)-(1R)-cis-chrysanthemic acid from Δ3-carene is reported.
- Dhillon, Ranjit S,Gautam, Veena K,Singh, Swaranjit,Singh, Jasvinder
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p. 574 - 578
(2007/10/02)
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- SYNTHESIS OF (1R)-(+)-CIS-CHRYSANTHEMIC ACID
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A synthesis of (1R)-(+)-cis-chrysanthemic acid from (R,R)-tartaric acid is described.The diol 8 was converted to the mono MEM protected compound 8b.Dehydration of the tertiary alcohol using methanesulfonyl chloride-triethylamine-DMAP and treatment of the resulting product with lithium in liquid ammonia afforded 10.The diazoester of 10 was subjected to intramolecular cyclopropanation using a soluble copper complex to obtain 12.Cleavage of the MEM ether, dehydration of the tertiary alcohol followed by reductive cleavage with lithium in liquid ammonia gave the title compound.
- Yadav, J. S.,Mysorekar, Sudha V.,Rao, A. V. Rama
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p. 7353 - 7360
(2007/10/02)
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- AN ASYMMETRIC SYNTHESIS OF BICYCLIC LACTONES AND ITS APPLICATION TO THE ASYMMETRIC SYNTHESIS OF (1R,3S)-CIS-CHRYSANTHEMIC ACID
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Optically active bicyclic lactones are synthesized from imides, derived from (R)-(-)-2-amino-2-phenylethanol and meso-cyclic-1,2-cis-dicarboxylic acids, by successive treatment with sodium bis(2-methoxyethoxy)aluminum hydride and sodium borohydride, followed by acid hydrolysis.This reaction is successfully applied to the asymmetric synthesis of (1R,3S)-cis-chrysanthemic acid.
- Mukaiyama, Teruaki,Yamashita, Hiroyuki,Asami, Masatoshi
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p. 385 - 388
(2007/10/02)
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- Deaminative Rearrangements of 1-Phenylthio- and 1-Oxy-Substituted Chrysanthemylamines
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Metalation of chrysanthemic nitrile 1 with lithium diisopropylamide followed by sulfenylation with diphenyl disulfide or oxygenation with a molybdenum peroxide complex gave chrysanthemic nitrile derivatives bearing phenylthio (3 and 4) or hydroxyl (6) substituents at C-1.These compounds provided access to the following series of 1-substituted chrysanthemylamines: 1-(phenylthio)chrysanthemylamine (5), 1-methoxychrysanthemylamine (8), 1-methoxydihydrochrysanthemylamine (10), and the N-nitrosooxazolidinone (13) derived from 1-hydroxychrysanthemylamine (11).Nitrous acid deamination of 5 and 8 and hydrolytic deamination of 13 gave acyclic alcohols (14, 17, and 18) related in structure to yomogi alcohol as major products by cleavage of the 1-3 cyclopropane ring bond.Products formed by cleavage of the 1-2 cyclopropane ring bond (15 and 24) and related in structure to santolinatriene were obtained in lesser amounts from the deamination of 5 and 13.Pinacol-type ring expansion to the isomeric cyclobutanones 19 and 20 was observed as a minor reaction pathway in the deaminations of 8 and 13.In contrast, deamination of 10 gave dihydrocyclobutanones 21 and 22 as the major isolated products.
- VanCantfort, Christopher K.,Coates, Robert M.
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p. 4331 - 4339
(2007/10/02)
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- Synthesis of Methyl 1R(+)-cis-Chrysanthemate and Methyl 1S(+)-cis-2,2-Dimethyl-3-(2-phenylprop-1-enyl)cyclopropane-1-carboxylate from (+)-Car-3-ene
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Synthesis of (+)-dihydrochrysanthemolactone (III), methyl 1R(+)-cis-chrysanthemate (II) and methyl 1S(+)-cis-2,2-dimethyl-3-(2-phenylprop-1-enyl)cyclopropane-1-carboxylate (XIII) has been achieved from a common intermediate 2,2-dimethyl-3-(2-methyl-2-hydroxypropyl)-cis-1-acetonylcyclopropane (IV), which is obtainable from (+)-car-3-ene by a known procedure.
- Bhat, N. G.,Mane, B. M.,Kulkarni, G. H.,Mitra, R. B.
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p. 204 - 206
(2007/10/02)
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- A NOVEL SYNTHESIS OF (+/-)-TRANS-CHRYSANTHEMIC ACID
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A novel approach to (+/-) trans chrysanthemic acid, from commercially avaiable 2,5-dimethyl-3-hexyne-2,5-diol /30 percent overall yield) is described.
- Genet, J.P.,Piau, F.,Ficini, J.
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p. 3183 - 3186
(2007/10/02)
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