- The identification of perillyl alcohol glycosides with improved antiproliferative activity
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A facile route to perillyl alcohol (POH) differential glycosylation and the corresponding synthesis of a set of 34 POH glycosides is reported. Subsequent in vitro studies revealed a sugar dependent antiproliferative activity and the inhibition of S6 ribos
- Nandurkar, Nitin S.,Zhang, Jianjun,Ye, Qing,Ponomareva, Larissa V.,She, Qing-Bai,Thorson, Jon S.
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- Oxidation of alcohols by TBHP in the presence of sub-stoichiometric amounts of MnO2
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Commercially available activated MnO2 has been investigated as a catalyst for the oxidation of alcohols (phenylethanol, 4-methyl- and 4-methoxybenzyl alcohol, trans-cinnamyl alcohol, cyclohexanol, menthol, perillyl alcohol and myrtenol) by TBHP/decane or TBHP/water in MeCN. The activity is highest for benzylic and allylic alcohols. Secondary alcohols yield ketones with good selectivities, while the aldehydes generated from primary alcohols are further oxidized. The process competes with the TBHP catalyzed decomposition. It thus requires the use of excess TBHP and high catalyst loadings to achieve high conversions. However, the low cost of the reagents makes this new protocol convenient for the oxidation of reactive secondary alcohols. The study also suggests that MnO2 should be proscribed as a reagent to quench excess TBHP in oxidative processes when the synthetic target contains easily oxidizable alcohol functions and when carrying our detailed kinetic monitoring of oxidation processes.
- Bhaumik, Chanchal,Stein, Dominique,Vincendeau, Sandrine,Poli, Rinaldo,Manoury, éric
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Read Online
- A new catalytic approach for aerobic oxidation of primary alcohols based on a Copper(I)-thiophene carbaldimines
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We report here novel Cu(I) thiophene carbaldimine catalysts for the selective aerobic oxidation of primary alcohols to their corresponding aldehydes and various diols to lactones or lactols. In the presence of the in situ generated Cu(I) species, a persistent radical (2,2,6,6-tetramethylpiperdine-N-oxyl (TEMPO)) and N-methylimidazole (NMI) as an auxiliary ligand, the reaction proceeds under aerobic conditions and at ambient temperature. Especially the catalytic system of 1-(thiophen-2-yl)-N-(4-(trifluoromethoxy)phenyl)methanimine (ligand L2) with copper(I)-iodide showed high reactivity for all kind of alcohols (benzylic, allylic and aliphatic). In the case of benzyl alcohol even 2.5 mol% of copper loading gave quantitative yield. Beside high activity under aerobic conditions, the catalysts ability to oxidize 1,5-pentadiol to the corresponding lactol (86% in 4 h) and N-phenyldiethanolamine to the corresponding morpholine derivate lactol (86% in 24 h) is particularly noteworthy.
- Lagerspets, Emi,Valbonetti, Evelyn,Eronen, Aleksi,Repo, Timo
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- Chemoselective hydrogen peroxide oxidation of primary alcohols to aldehydes by a water-soluble and reusable iron(iii) catalyst in pure water at room temperature
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Hydrogen peroxide oxidation of primary alcohols to aldehydes is described, which is catalyzed by a novel, reusable and water-soluble FeCl3 complex in situ-formed with quaternary ammonium salt-functionalized 8-aminoquinoline. This reaction exhibits unique chemoselectivity and broad functional-group tolerance, and it can operate efficiently in pure water at room temperature.
- Yan, Qi,Fang, Ye Chen,Jia, Yun Xue,Duan, Xin Hong
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p. 2372 - 2377
(2017/03/21)
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- Evaluation of antiparasitic activity of mentha crispa essential oil, its major constituent rotundifolone and analogues against trypanosoma brucei
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Considering the pressing need for new drugs to treat sleeping sickness and Nagana disease, Mentha crispa essential oil, its principal constituent rotundifolone, and four related p-menthane-Type monoterpenes (two stereoisomers of limonene epoxide, perillyl alcohol, and perillyl aldehyde) were investigated for their activity against bloodstream forms of Trypanosoma brucei. The general cytotoxicity of the compounds was determined with human myeloid HL-60 cells. The effect of the M. crispa essential oil and the monoterpenes on the growth of parasite and human cells was evaluated in cell cultures with the resazurin viability assay. Of all of the compounds tested, M. crispa essential oil, rotundifolone, and perillyl aldehyde showed the highest trypanocidal activities with 50% growth inhibition (GI50) and minimum inhibitory concentration values of 0.3 μg/ mL and 1 μg/mL, respectively. In contrast, HL-60 cells were considerably less sensitive to the compounds with minimum inhibitory concentration values of 100 μg/mL and GI50 values ranging between 3.4 to 13.8 μg/mL. As a consequence of this, GI50 and minimum inhibitory concentration ratios of cytotoxic to trypanocidal activity (selectivity index) of these three compounds were promising with values of 11-45 and 100, respectively. These results indicate that the p-menthane-Type monoterpenes rotundifolone and perillyl aldehyde are interesting lead candidates for further rational antitrypanosomal drug development.
- De Sousa, Dami?o Pergentino,Lima, Tamires Cardoso,Steverding, Dietmar
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p. 1346 - 1350
(2016/10/24)
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- Enzyme-inspired functional surfactant for aerobic oxidation of activated alcohols to aldehydes in water
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We describe an enzyme-inspired catalytic system based on a rationally designed multifunctional amphiphile. The resulting micelles feature metal-binding sites and stable free radical moieties as well as fluorous pockets that attract and preconcentrate molecular oxygen. In the presence of copper ions, the micelles effect chemoselective aerobic alcohol oxidation under ambient conditions in water, a transformation that is challenging to achieve nonenzymatically.
- Chen, Ba-Tian,Bukhryakov, Konstantin V.,Sougrat, Rachid,Rodionov, Valentin O.
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p. 1313 - 1317
(2015/02/19)
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- Solar photochemical oxidations of benzylic and allylic alcohols using catalytic organo-oxidation with DDQ: Application to lignin models
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Visible light has a dramatic effect on the oxidation of benzylic and allylic alcohols, including those deactivated by electron-withdrawing groups, and β-O-4 lignin models, using catalytic amounts of the organo-oxidant 2,3-dichloro-5,6-dicyano-1,4-benzoquinone. Sodium nitrite or tert-butyl nitrite is used as cocatalyst, and oxygen is employed as the terminal oxidant.
- Walsh, Katie,Sneddon, Helen F.,Moody, Christopher J.
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supporting information
p. 5224 - 5227
(2014/12/11)
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- Solar photochemical oxidation of alcohols using catalytic hydroquinone and copper nanoparticles under oxygen: Oxidative cleavage of lignin models
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Alcohols are converted into to their corresponding carbonyl compounds using catalytic amounts of 1,4-hydroquinone with a copper nanoparticle electron transfer mediator with oxygen as the terminal oxidant in acetone as solvent under visible light irradiation. These conditions employing biorenewable hydroquinone as reagent were developed from initial experiments using stoichiometric amounts of 1,4-benzoquinone as oxidant. A range of benzylic and aliphatic primary and secondary alcohols are oxidized, affording the corresponding aldehydes or ketones in moderate to excellent yields. The methodology is also applicable to the oxidative degradation of lignin model compounds that undergo C-C bond cleavage to give simple aromatic compounds.
- Mitchell, Lorna J.,Moody, Christopher J.
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p. 11091 - 11100
(2015/01/08)
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- Selective aerobic oxidation of allylic and benzylic alcohols catalyzed by N-hydroxyindole and copper(I) chloride
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In the presence of copper(I) chloride, tert-butyl 1-hydroxy-2-methyl-6- trifluoromethyl-1H-indole-3-carboxylate acted as a catalyst for the chemoselective aerobic oxidation of allylic and benzylic alcohols. A variety of primary and secondary allylic and benzylic alcohols were oxidized into the corresponding α,β-unsaturated carbonyl compounds in good yields without affecting non-allylic alcohols.
- Shen, Shu-Su,Kartika, Vita,Tan, Ying Shan,Webster, Richard D.,Narasaka, Koichi
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supporting information; experimental part
p. 986 - 990
(2012/03/12)
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- One-pot chemoenzymatic synthesis of aldoximes from primary alcohols in water
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A new synthetic method for the one-pot preparation of aldoximes in water was developed; the method is based on the combination of the enzymatic oxidation of primary alcohols to aldehydes using different acetic acid bacteria and in situ condensation of the aldehydes with hydroxylamine.
- Zambelli, Paolo,Pinto, Andrea,Romano, Diego,Crotti, Elena,Conti, Paola,Tamborini, Lucia,Villa, Raffaella,Molinari, Francesco
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body text
p. 2158 - 2161
(2012/09/22)
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- α,β-Unsaturated imines via Ru-catalyzed coupling of allylic alcohols and amines
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A convenient synthesis of α,β-unsaturated imines requiring only an allylic alcohol, an amine and a Ru catalyst has been developed. The use of large excesses of oxidant and the purification of sensitive intermediates can be avoided.
- Rigoli, Jared W.,Moyer, Sara A.,Pearce, Simon D.,Schomaker, Jennifer M.
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p. 1746 - 1749
(2012/04/23)
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- A simple method for the oxidation of primary alcohols with o-iodoxybenzoic acid (IBX) in the presence of acetic acid
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A simple method for the oxidation of primary alcohols to aldehydes using o-iodoxybenzoic acid (IBX) with the addition of stoichiometric acetic acid has been developed. Addition of acetic acid significantly accelerated the reaction rate. Under these conditions, primary aliphatic, benzylic, and allylic alcohols are smoothly converted to aldehydes in high yields (90-97%).
- Lin, Cheng-Kun,Lu, Ta-Jung
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experimental part
p. 9688 - 9693
(2011/02/24)
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- Catalytic activity dependency on catalyst components in aerobic copper-TEMPO oxidation
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The influence of catalyst components in the copper-TEMPO (2,2,6,6-tetramethylpiperidine N-oxide) catalysed aerobic oxidation of alcohols was investigated. The type and amount of base greatly influences reactivity. The bipyridyl ligand concentration had no major influence on catalysis, but ex-cessive amounts led to a decrease in activity for longer reaction times. The kinetic dependency for TEMPO was found to be 1.15, and for copper 2.25, which is an indication of a binuclear catalytic system. Optimised conditions with various allylic and aliphatic alcohols give good to excellent rapid oxidations.
- Kumpulainen, Esa T. T.,Koskinen, Ari M. P.
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experimental part
p. 10901 - 10911
(2010/04/05)
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- A chemoenzymatic, preparative synthesis of the isomeric forms of p-menth-1-en-9-ol: Application to the synthesis of the isomeric forms of the cooling agent 1-hydroxy-2,9-cineole
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A preparative-scale synthesis of the four p-menth-1-en-9-ol isomers 2a-5a has been achieved by means of two chemoenzymatic processes. Both synthetic pathways start from the enantiomeric forms of limonene that are converted into p-mentha-1,8-dien-9-al isomers 12 and 15. The baker's yeast mediated reduction of the latter aldehydes afforded compounds 3a and 5a, respectively, with very high enantioselectivity. Moreover, chemical reduction of 12 and 15 gives the mixtures of enantiopure diastereoisomers 2a/3a and 4a/5a, respectively. PPL (Porcine pancreas lipase) mediated resolution of the latter mixtures followed by fractionating crystallization of derivatives 2b-5b allowed the enantio- and diastereoisomerically pure alcohols 2a-5a to be obtained. Compounds 2a-5a have then been used as starting materials for the preparation of four isomers of the cooling agent 1-hydroxy-2,9-cineole (6-9). Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
- Serra, Stefano,Fuganti, Claudio,Gatti, Francesco G.
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experimental part
p. 1031 - 1037
(2009/04/05)
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- A Mild and Efficient Oxidation of Alcohols to Carbonyl Compounds by Periodic Acid Catalyzed by 2,2,6,6-Tetramethylpiperidinyl-1-oxyl
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Numerous alcohols are effectively oxidized to corresponding aldehydes and ketones with H5IO6-TEMPO. The rate of oxidation parallels decreasing α-C-H bond dissociation energy, that is secondary alcohols react faster than primary alcohols.
- Kim, Sung Soo,Nehru, Kasi
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p. 616 - 618
(2007/10/03)
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- Synthesis and reactions of organic compounds with a nitrogen atom. Part XVII. Reactions of acyclic and monocyclic chlorides with phenyltelluro- and phenylselenosodium
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The reaction of neryl (3), geranyl (4), (+)-carvotanacetyl (5), (-)-carvyl (6) and perillyl (7) chlorides with phenylseleno-(1) or phenyltellurosodium (2), and then with chloramine-T afforded α,β-unsaturated toluenesulfonamides 8-11, which were reduced with sodium in liquid ammonia to allylic amines 12-15. Allylic phenyltellurides were oxidized by air to carbonyl compounds 29-31 or alcohol 28.
- Bakowska-Janiszewska,Scianowski,Uzarewicz
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p. 649 - 656
(2007/10/03)
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- The synthesis and oxidative properties of polymer-supported IBX
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Primary and secondary alcohols are oxidized smoothly under mild conditions and in high yields to the corresponding aldehydes and ketones by 1 (see scheme), the first polymer-supported IBX.
- Muelbaier,Giannis
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p. 4393 - 4394
(2007/10/03)
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- Deblocking of dithioacetals and oxathioacetals using periodic acid under mild nonaqueous conditions
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A novel method for the deblocking of the dithioacetals and oxathioacetals is described. Periodic acid under nonaqueous conditions has been used for the deprotection of the dithio- and oxathio-derivatives to the corresponding carbonyl compounds. This simple high-yield transformation is conveniently carried out in nonaqueous medium and works well with complex sensitive aldehydes and in the presence of other protective groups.
- Shi, Xiao-Xin,Khanapure, Subhash P.,Rokach, Joshua
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p. 4331 - 4334
(2007/10/03)
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- 7,9-dihydroxy-1,8-cineole and 2α,7-dihydroxy- 1,8-cineole: Two new possum urinary metabolites
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Chemical syntheses for 7,9-dihydroxy-1,8-cineole (8a) and 2α,7-dihydroxy-1,8-cineole (9a) are reported. These products are identical with the urinary metabolites isolated from brushtail possums fed 1,8-cineole (1) and 2α-hydroxy-1,8-cineole (4) respectively.
- Carman, Raymond M.,Garner, A. Christopher
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p. 741 - 749
(2007/10/03)
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- The oxidation of allylic methylene groups under FeIII-TBHP and FeIII-TBHP-PA conditions
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Oxidation of allylic methylene groups under FeIII-TBHP (FeIII-t-butyl hydroperoxide) and FeIII-TBHP-PA (FeIII-t-butyl hydroperoxide-picolinic acid) conditions gave α- and γ-ketonization products.
- Barton, Derek H. R.,Wang, Tie-Lin
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p. 4307 - 4310
(2007/10/02)
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- Enantioselective synthesis of chiral liquid crystalline compounds from monoterpenes
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Chiral liquid crystalline compounds 1-9 have been synthesized enantioselectively from monoterpenes. The optical purities of (S)-(-)- and (R)-(+)-perillalcohol (16, 27), (S)-(-)- and (R)-(+)-1-pentyl-4-hydroxymethyl-1-cyclohexene (33, 34) and (2S,5S)-2-pentyl-5-hydroxymethyl-1-cyclohexanone (53) have been determined by 1H NMR analysis using chiral shift reagents. The mesomorphic phases and transition temperatures of compounds 2,3,5,6,7,8 and 9 have been characterized.
- Wang, Qian,Fan, Shi Yan,Wong, Henry N. C.,Li, Zhong,Fung, Bing M.,Twieg, Robert J.,Nguyen, Huu Tinh
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p. 619 - 638
(2007/10/02)
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- The Action of Sodium Nitrite-Acetic Acid on α- and β-Pinene. Participation by Neighbouring Geminal Dinitro Group in the Base-catalysed Epimerization of a Secondary Alcohol
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The reaction of (-)-α-pinene (1) with sodium nitrite-acetic acid gave principally (2S,4R)-2-nitromentha-1(6),8-diene (2) and smaller amounts of (2S,4R)-2-nitromenth-1(6)-en-8-yl acetate (3), (1R,4S)-2-endo-nitrato-6-endo-nitrobornane (4), (1S,4R)--3,3-dimethyl-2-endo-nitrato-6-exo-nitro-8,9-dinorbornane (5), and (-)-3-nitropin-2-ene (6).A similar reaction with (-)-β-pinene (8) afforded (4S)-7-nitromentha-1,8-diene (9) as the major product and (4S)-7-nitromenth-1-en-8-yl acetate (10), (1S,4S)-2-endo-nitrato-10-nitrobornane (11), and (1R,4S)-3,3-dimethyl-2-endo-nitrato-10-nitro-8,9-dinorbornane (12) in lower yields.Treatment of the nitro-nitrates (11) and (12) in basic medium gave the corresponding 10,10-dinitro alcohols (20) anfd (21) by intramolecular transfer of the nitro group with retention of configuration at C-2.In stronger alkaline conditions the dinitro endo-alcohol (21) produced unexpectedly the epimeric exo-alcohol (22).The neighbouring participation of the 10,10-dinitro qroup is shown to be essential for the epimerization to take place.Plausible mechanisms for these reactions are proposed.
- Francisco, Cosme G.,Freire, Raimundo,Hernandez, Rosendo,Melian, Daniel,Salazar, Jose A.,Suarez, Ernesto
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p. 459 - 465
(2007/10/02)
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- Synthese von (-)-Spathulenol
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In reference to the famous synthesis of (-)-aromadendrene, the synthesis of (-)-spathulenol (31) and (-)-7-epi-spathulenol (32) from (-)-β-pinene via (-)-perillaaldehyde and the intermediates 7, 19 and 25 is described.
- Surburg, Horst,Mondon, Albert
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p. 118 - 131
(2007/10/02)
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