- Chiral Titanium(IV) Complexes Containing Polydentate Ligands Based on α-Pinene. Catalytic Activity in Sulfoxidation with Hydrogen Peroxide
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The reaction of TiCl4-n(OiPr)n (n = 0, 2, 4) with various terpenoid preligands based on α-pinene, C7H6Me3(OH)(NCH2CH2G) (G = NH2, I; NHMe, II; OH, III), stereoselectively affords a series of new chiral titanium(IV) complexes. Such complexes are either octahedral, [TiCl2X(OC7H6Me3NCH2CH2G-κ3N,N,O)] (X = Cl, G = NH2, 1; X = OiPr, G = NH2, 2; G = NHMe, 3), or trigonal bipyramidal, [Ti(OiPr)3(OC7H6Me3NCH2CH2G-κ2N,O)] (G = NH2, 4; NHMe, 5) and [TiX(OiPr)(OC7H6Me3NCH2CH2O-κ3N,O,O?)] (X = Cl, 6; OiPr, 8), depending on the acidity of titanium, the reaction conditions and the nature of the pendant ending group of the terpenoid ligand. Density functional theory (DFT) calculations have been carried out to assess the stability of the multiple possible diastereoisomers allowing us to propose structural suggestions. The new titanium complexes efficiently catalyze the selective oxidation of various types of sulfides to either sulfoxides or sulfones using aqueous hydrogen peroxide, under mild conditions. All compounds have been characterized by multinuclear NMR spectroscopy and the molecular structure for some of them has been determined by X-ray diffraction.
- Reviejo, Irene,Tabernero, Vanessa,Mosquera, Marta E. G.,Ramos, Javier,Cuenca, Tomás,Jiménez, Gerardo
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p. 3437 - 3449
(2018/10/31)
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- Synthesis and characterization of new palladium complexes based on polydentate chiral Schiff base and amines ligands derived from (+)-2-hydroxypinan-3-one
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Seven novel palladium complexes of the type [Pd(HL)Cl2] and [Pd(L)Cl] containing chiral pinane ligands (HL = 3-[(2-aminoethyl)imino]-pinane-2-ol; 3,3′-(ethylenediimino)bis-pinane-2-ol; cis-3-(2-aminoethylamino)-pinane-2-ol; cis-3,3′(ethylenediamino)bis-pinane-2-ol; trans-3,3′(ethylenediamino)bis-pinane-2-ol; 3-[2-(2-hydroxybenzylamino)ethylamino]-pinane-2-ol; L = 3-[2-(3,5-di-tert-butyl-2-hydroxybenzylidene)aminoethylimino]pinane-2-ol) were synthesized in good yields from the direct reaction of chiral nitrogen ligands with Li2PdCl4 in MeOH. These synthesized complexes were characterized by means of elemental analysis, FT-IR, multidimensional and multinuclear NMR spectroscopic methods.
- Gur'eva, Yana A.,Alekseev, Igor N.,Dvornikova, Irina A.,Zalevskaya, Olga A.,Kuchin, Aleksandr V.
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p. 300 - 305
(2018/11/21)
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- Synthesis and physical chemical properties of 2-amino-4-(trifluoromethoxy)butanoic acid-a CF3O-containing analogue of natural lipophilic amino acids
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2-Amino-2-(trifluoromethoxy)butanoic acid (O-trifluoromethyl homoserine) was synthesized as a racemate and in both enantiomeric forms. The measured pKa and log D values establish the compound as a promising analogue of natural aliphatic amino acids.
- Kondratov, Ivan S.,Logvinenko, Ivan G.,Tolmachova, Nataliya A.,Morev, Roman N.,Kliachyna, Maria A.,Clausen, Florian,Daniliuc, Constantin G.,Haufe, Günter
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p. 672 - 679
(2017/01/25)
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- New chiral ligands derived from (+) and (-)-α-pinene for the enantioselective addition of diethylzinc to aldehydes
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In this study, we synthesized five new chiral ligands from (+) and (-)-α-pinene, which were successfully employed in the stereoselective addition of diethylzinc to aldehydes, leading to secondary chiral alcohols in up to 99% yield and 94% e.e.
- Frensch, Gustavo,Labes, Ricardo,Wosch, Celso Luiz,Munaretto, Laieli Dos Santos,Salomé, Kahlil Schwanka,Guerrero, Palimécio G.,Marques, Francisco A.
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p. 420 - 422
(2016/01/12)
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- NOVEL SYNTHESIS INTERMEDIATES FOR OBTAINING DERIVATIVES OF SPHINGOSINES, CERAMIDES AND SPHINGOMYELINS WITH GOOD YIELDS
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The subject matter of the present invention is the novel molecules of formulae E, E′ and F. These molecules prove to be synthesis intermediates that are very advantageous for the manufacture of derivatives of sphingosine or of ceramides functionalized in position 1, with good yields, in which R1 and R2 are fatty chains, R3 is an alkyl group and R4 is a protective group for alcohol functions. Another subject of the invention is the use of the intermediates of type F for converting same into intermediates of type G, by means of reduction in the presence of lithium borohydride. The G molecules are precursors that are known to make it possible to obtain sphingolipids or sphingomyelin.
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- Synthesis of chiral 1,2-diamines from α-pinene and their use in asymmetric nitroaldol reaction
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Abstract Chiral diamines with C 1 and C 2 symmetry have been synthesized from 2-hydroxypinan-3-one and tested as ligands in Cu-catalyzed asymmetric nitroaldol reaction of nitromethane with 4-nitrobenzaldehyde.
- Dvornikova,Buravlev,Suponitskii,Chukicheva,Kutchin
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p. 480 - 492
(2015/05/27)
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- New chiral cyclopalladated complexes based on the pinane and bornane imines
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2α-Hydroxypinan-3-one imino derivatives react with lithium tetrachloropalladate to form palladacycles, while similar bornane derivative undergo cyclopalladation only when treated with palladium acetate.
- Kuchin,Gur'eva,Frolova,Alekseev,Zalevskaya
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p. 745 - 750
(2014/01/23)
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- Novel α-pinene-derived mono- and bisphosphinite ligands: Synthesis and application in catalytic hydrogenation
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Novel mono- and bisphosphinite (-)-pinane-based ligands have been synthesized from (-)-α-pinene. Mixed with [(COD)2Rh] +[BF4]-, these ligands displayed moderate up to high catalytic activity in hydrogenation of dimethyl itaconate with dihydrogen. It has been observed that the structure of the ligand, the reaction temperature and solvent are important to define productivity of the phosphinite-based Rh-catalysts. Bisphosphinite ligands in hydrogenation reactions suffered from an Arbuzov rearrangement, leading to fast deactivation of the hydrogenation catalyst. In contrast, monophosphinite-derived Rh-catalysts showed increased productivity as well as thermal stability. An almost quantitative conversion of dimethyl itaconate has been achieved at elevated temperatures in toluene. Alternatively, hydrogenation of dimethyl itaconate with monophosphinite ligands has been carried out in MeOH at room temperature or 40 °C and has led to a nearly quantitative conversion.
- Hobu?, Dennis,Hasenj?ger, Jens,Driessen-H?lscher, Birgit,Baro, Angelika,Axenov, Kirill V.,Laschat, Sabine,Frey, Wolfgang
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scheme or table
p. 94 - 103
(2011/09/15)
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- Chiral imines and amines based on 2-hydroxypinan-3-one
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The new chiral derivatives of benzylamine and 2α-hydroxypinan-3-one (1R,2R,5R)-3-[(1S)-α-methylbenzylamino]-2,6,6-trimethylbicyclo[3.1.1] heptan-2-ol (2), (1S,2S,3S,5S)-3-(benzylamino)-2,6,6-trimethylbicyclo[3.1.1] heptan-2-ol (3), and (1R,2R,3R,5R)-3-[(1S)-α-methylbenzylamino]-2,6,6- trimethylbicyclo[3.1.1]heptan-2-ol (4) were synthesized and characterized. It was shown that reduction of the benzylimines by sodium triacetoxyborohydride formed stereoselectively 3β-substituted pinanamines.
- Gur'eva,Zalevskaya,Frolova,Alekseev,Kuchin
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body text
p. 920 - 923
(2011/05/04)
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- Synthesis of 1,2-diamine ligands based on natural monoterpenoids
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New nitrogen-containing chiral ligands were synthesized containing terpene fragments of pinane and camphane structure.
- Dvornikova,Buravlev,Frolova,Nelyubina,Chukicheva,Kuchin
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experimental part
p. 1130 - 1138
(2011/11/30)
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- Metabolism and mode of action of cis- and trans-3-pinanones (the active ingredients of hyssop oil)
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1. Hyssop oil is an important food additive and herbal medicine and the principal active ingredients are (-)-cis- and (-)-trans-3-pinanones. No information is available on their metabolism or specific mode of action. 2. The metabolites of cis- and trans-3-pinanones were examined from mouse and human liver microsomes and human recombinant P4503A4 with NADPH and on administration to mouse by gas chromatography/chemical ionization mass spectrometry comparison with standards from synthesis. 3. The major metabolite of cis-3-pinanone in each P450 system and in brain of the i.p.-treated mouse in quantitative studies was 2-hydroxy-cis-3-pinanone, and two minor metabolites were hydroxypinanones other than 2-hydroxy-trans-3-pinanone and 4S-hydroxy-cfs-3-pinanone. The urine from oral cis-3-pinanone treatment examined on a qualitative basis contained conjugates of metabolites observed in the microsomal systems plus 2,10-dehydro-3-pinanone. 4. Trans-3-pinanone was metabolized more slowly than the cis-isomer in each system to give hydroxy derivatives different than those derived from cis-3-pinanone. 5. Cis- and trans-3-pinanones and hyssop oil act as γ-aminobutyric acid type A (GABAA) receptor antagonists based on inhibition of 4′-ethynyl-4-n-[2,3-3H2] propylbicycloorthobenzoate ([3H]EBOB) binding in mouse brain membranes (IC50 of 35-64μM) and supported by tonic/clonic convulsions in mouse (i.p. LD50 175 to >250 mg kg-1) alleviated by diazepam. The cis-3-pinanone metabolites 2-hydroxy-cis-3-pinanone and 2,10-dehydro-3-pinanone exhibit reduced toxicity and potency for inhibition of [3H]EBOB binding.
- Hoeld,Sirisoma,Sparks,Casida
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p. 251 - 265
(2007/10/03)
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- Asymmetric synthesis of α-cycloalkylalkyl substituted methanamines
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This invention relates to process for asymmetrically producing enantiomerically pure α-cycloalkylalkyl substitututed methanamines from α-pinene. One key step of the process of this invention utilizes the oxidation product of α-pinene, hydroxy pinanone, as a chiral auxiliary to direct the stereoselective alkylation of the corresponding ketimine. This invention also relates to key intermediates useful in the processes referred to herein.
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- Enantioselective Synthesis of γ-Hydroxynorvaline
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A new synthesis of enantiomerically pure γ-hydroxynorvaline is described. The key step involves diastereoselective alkylation of the chiral Schiff base 1 with primary iodo derivatives 2 easily prepared from propylene oxide.
- Jacob,Roumestant,Viallefont,Martinez
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p. 691 - 692
(2007/10/03)
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- Ruthenium Tetroxide Oxidation of Alkenes. A More Complete Picture
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The ruthenium tetroxide oxidation of some linear and cyclic alkenes, representatives of five substitution patterns, has been performed in acetone-water (5:1) solution at -70 deg C using stoichiometric ammounts of the oxidant.The main reaction products are 1,2-diols and/or α-ketols depending on the nature of the substrate little amounts of scission products, aldehydes and/or carboxylic acids, are also obtained.Generally 1,2-diols predominate over α-ketols except in the oxidation of (-)-α-pinene that afforded the α-ketol in 51percent yield while no trace of the corresponding 1,2-diol was detected.All reactions prceeded through the formation of unstable brownish precipitates, presumably the intermediate ruthenium (VI) esters, which easily decomposed during the work-up step.Results from oxidation of trans-7-tetradecene and cis and trans-11-tetradecenyl acetate indicated that the reaction was syn stereospecific.In some cases, 1,3-dioxolane products, formed by condensation of the 1,2-diol and the aldehyde materials, were also obtained among the reaction products.Their possible origin is briefly discussed.
- Albarella, Laura,Piccialli, Vincenzo,Sica, Donato,Smaldone, Dina
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p. 2442 - 2456
(2007/10/03)
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- A practical method for preparation of optically pure oxazaborolidines from α-pinene
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(1S,2S,3R,5S)- and (1S,2S,3R,5S)-3-amino-2-hydroxypinane (1 and 2) were prepared from the corresponding α-pinene in optically pure form. They and their derivatives reacted with various organoborane compounds. A variety of chiral oxazaborolidines 3a-e and 4 were obtained in high yield.
- Masui, Moriyasu,Shioiri, Takayuki
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p. 8363 - 8370
(2007/10/02)
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- Evidence for the existence of a cyclic ruthenium (VI) diester as an intermediate in the oxidative scission of (-)-α-pinene with RuO4
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The reaction of (-)-α-pinene (1) with RuO4 in CCl4 at room temperature affords the ketoaldehyde 3 as the sole product. Evidence is reported that the oxidative scission of the olefinic substrate to 3 proceeds through a ruthenium (VI) diester intermediate for which we propose structure 2 on the basis of spectral evidence and comparison with the osmium-containing analogue of 2, synthesised by reaction of (-)-α-pinene with OsO4 in dioxane and whose structure has been determinated by single crystal X-ray diffraction analysis. Compound 2 was also shown to be an intermediate compound in the RuO4 oxidation of (-)-α-pinene performed in acetone-water (2:1) which gives α-ketol 4 as the sole oxidation product.
- Albarella, Laura,Giordano, Federico,Lasalvia, Maria,Piccialli, Vincenzo,Sica, Donato
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p. 5267 - 5270
(2007/10/02)
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- A new asymmetric synthesis of (S)-dolaphenine and its heteroaromatic congeners utilizing (+)-2-hydroxy-3-pinanone and (-)-3-hydroxy-2-caranone as chiral auxiliaries
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(+)-2-hydroxy-3-pinanone ((+)-HyPN,(+)-2a) and (-)-3-hydroxy-2-caranone ((-)-2b) were respectively converted to the corresponding Schiff bases 18a and 18b with 1-(2-thiazolyl)methylamine (17). Alkylation followed by removal of the chiral auxiliaries (+)-2a and (-)-2b afforded (S)-dolaphenine (10) as an optically pure form. The method was applied to the asymmetric synthesis of the dolaphenine analogs 27a-d.
- Irako, Naoko,Hamada, Yasumasa,Shioiri, Takayuki
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p. 12731 - 12744
(2007/10/02)
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- The Baeyer-Villiger reaction of pinanones (bicyclo[3.1.1]heptanones)
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The Baeyer-Villiger reaction of bicyclo[3.1.1]heptanones yields the expected lactones, but with some difficulty. These lactones readily react with alcohols, including the ethanol present in commercial chloroform, to give the corresponding hydroxy esters. Pinocamphone and isopinocamphone exhibit conformational control in the Baeyer-Villiger reaction, the trans-isomer yielding mainly the expected lactone, the cis-isomer (isopinocamphone) yielding hydroxyisopinocamphone. The use of this pathway as a synthetic route to cyclobutane monoterpenoids is discussed.
- Thomas,Rey
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p. 1927 - 1942
(2007/12/18)
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- ASYMMETRIC SYNTHESIS OF (+)-PHOSPHINOTHRICIN and (+)-2-AMINO-4-PHOSPHONOBUTYRIC ACID
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Asymmetric synthesis of (+)-phosphinothricin, (+)-2-amino-4-phosphono-butyric acid, and their enantiomers has been achieved by the Michael addition of chiral glycine Schiff bases to vinyl phosphorus compounds.
- Minowa, Nobuto,Hirayama, Masao,Fukatsu, Shunzo
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p. 1147 - 1150
(2007/10/02)
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