- Facile synthesis of 5-Hexyl-4-methyl-γ-butyrolactone via Nef reaction as a key step
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A racemic cis/trans mixture of 5-hexyl-4-methyl-γ-butyrolactone was easily synthesized from 1-iodoheptane in four steps with inexpensive and readily available reagents. Our new synthesis method can be potentially employed for mass production of the 4-methyl-5-hexyl-γ-butyrolactone as well as other poly-alkyl substituted γ-butyrolactones.
- Li, Zhi,Wang, Changwei,Feng, Pengju
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- Synthesis of 9- and 12-nitro conjugated linoleic acid: Regiospecific isomers of naturally occurring conjugated nitrodienes
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Conjugated diene-containing fatty acids (rumenic and rumelenic acids) are major substrates for nitration under physiological conditions. Their nitrated products are present in human urine. These nitrodiene-containing lipid electrophiles contain a strongly electron-withdrawing pair of conjugated double bonds amenable to nucleophilic attack in biological milieu, which affords them pluripotent signaling capabilities. We report synthetic methods to obtain useful quantities of three main biological nitrated fatty acids (9- and 12-nitro-conjugated linoleic acids and 9-nitro-conjugated linolenic acid) in six or seven steps from commercially available starting materials, for biological evaluation of these naturally occurring biomolecules.
- Woodcock, Steven R.,Salvatore, Sonia R.,Freeman, Bruce A.,Schopfer, Francisco J.
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supporting information
(2021/09/13)
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- Crystallization Does It All: An Alternative Strategy for Stereoselective Aza-Henry Reaction
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An efficient and experimentally straightforward method for the stereoselective synthesis of a variety of β-nitro-α-amino carboxylic acids via aza-Henry (nitro-Mannich) reaction of aldimines is disclosed, yielding either anti- or a rarely reported syn-configuration. The reaction operates directly on free glyoxylic acid and generates imine species in situ. Crystallization-controlled diastereoselectivity enables isolation of the target compounds in high enantio- and diastereomeric purities by a simple filtration.
- Mar?eková, Michaela,Ger?a, Peter,?oral, Michal,Moncol, Ján,Berke?, Du?an,Kolarovi?, Andrej,Jakubec, Pavol
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supporting information
p. 4580 - 4584
(2019/06/17)
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- Easy and direct conversion of tosylates and mesylates into nitroalkanes
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Tosylates and mesylates were directly converted into the corresponding nitroalkanes, by their treatment with tetrabutylammonium nitrite (TBAN) under mild conditions.
- Palmieri, Alessandr,Gabrielli, Serena,Ballini, Roberto
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p. 533 - 536
(2013/04/24)
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- Henry reaction of fluorinated nitro compounds
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The Henry (nitroaldol) reaction of fluorinated nitro compounds with various aromatic aldehydes and a fluorinated aliphatic aldehyde to give β-fluoro-β-nitroalcohols which bearing a fluorinated quaternary carbon center was reported. The relative configuration of the major diastereoisomer of 2-fluoro-2-nitro-1-(4-nitrophenyl)-3-phenylpropanol (5bf) was determined by X-ray single crystal analysis.
- Hu, Huawei,Huang, Yangen,Guo, Yong
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experimental part
p. 108 - 114
(2012/02/05)
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- Visible-light-promoted C-C bond cleavage: Photocatalytic generation of iminium ions and amino radicals
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Photoscissors: Structurally variable and synthetically robust iminium ions and amino radicals species could be simultaneously generated by visible-light-promoted photoredox cleavage of the C-C bonds in simple vicinal diamine precursors under very mild reaction conditions. Copyright
- Cai, Shunyou,Zhao, Xinyang,Wang, Xinbo,Liu, Qisong,Li, Zigang,Wang, David Zhigang
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p. 8050 - 8053
(2012/08/29)
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- Mild oxidative conversion of nitroalkanes into carbonyl compounds in ionic liquids
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Basic hydrogen peroxide and sodium perborate were found to be cheap and efficient alternatives for the conversion of primary and secondary nitro to carbonyl compounds (Nef reaction) in ionic liquids. Copyright Taylor & Francis Group, LLC.
- Bortolini, Olga,Nino, Antonio De,Garofalo, Angelo,Maiuolo, Loredana,Russo, Beatrice
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experimental part
p. 2483 - 2487
(2010/09/07)
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- Activation of Peroxisome Proliferator-Activated Receptor γ (PPARγ) by nitroalkene fatty acids: Importance of nitration position and degree of unsaturation
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Nitroalkene fatty acids are potent endogenous ligand activators of PPARγ-dependent transcription. Previous studies with the naturally occurring regioisomers of nitrolinoleic acid revealed that the isomers are not equivalent with respect to PPARγ activation. To gain further insight into the structure-activity relationships between nitroalkenes and PPARγ, we examined additional naturally occurring nitroalkenes derived from oleic acid, 9-nitrooleic acid (E-9-NO2-18:1 [1]) and 10-nitrooleic acid (E-10-NO2-18:1 [2]), and several synthetic nitrated enoic fatty acids of variable carbon chain length, double bonds, and nitration site. At submicromolar concentrations, E-12-NO2 derivatives were considerably more potent than isomers nitrated at carbons 5, 6, 9, 10, and 13, and chain length (16 versus 18) or number of double bonds (1 versus 2) was of little consequence for PPARγ activation. Interestingly, at higher concentrations (>2 μM) the nitrated enoic fatty acids (E-9-NO2-18:1 [1], E-9-NO2-16:1 [3], E-10-NO2-18:1 [2], and E-12-NO 2-18:1 [7]) deviated significantly from the saturable pattern of PPARγ activation observed for nitrated 1,4-dienoic fatty acids (E-9-NO2-18:2, E-10-NO2-18:2, E-12-NO2-18:2, and E-13-NO2-18:2).
- Gorczynski, Michael J.,Smitherman, Pamela K.,Akiyama, Taro E.,Wood, Harold B.,Berger, Joel P.,King, S. Bruce,Morrow, Charles S.
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experimental part
p. 4631 - 4639
(2010/03/01)
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- Scope and mechanistic insights into the use of tetradecyl(trihexyl) phosphonium bistriflimide: A remarkably selective ionic liquid solvent for substitution reactions
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A survey of substitution reactions conducted in a phosphonium bistriflimide ionic liquid is presented. The results demonstrate high selectivity favoring substitution over typically competitive elimination and solvolytic processes even when challenging secondary and tertiary electrophiles are employed. The first reports of Kornblum substitution reactions in an ionic liquid are described that proceed with very high chemoselectivity in favor of nitro over nitroso products and elimi nation side products. The structure-reactivity study indicates that these reactions proceed through a narrow spectrum of pathways ranging from straight SN2 to a preassociation pathway along a saddle point that approaches the SN1 limit. The barrier to the formation of dissociated carbocations is attributed to the structural features of this ionic liquid that favor intervention of the associated nucleophile over dissociation, also preventing cross over to E1 processes. The lack of any basic entity in the phosphonium bistriflimide ionic liquid appears to prevent any potential base-mediated elimination reactions, which makes this a highly selective medium for use in general substitution reactions.
- McNulty, James,Nair, Jerald J.,Cheekoori, Sreedhar,Larichev, Vladimir,Capretta, Alfredo,Robertson
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p. 9314 - 9322
(2007/10/03)
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- SYNTHESIS OF LOW-MOLECULAR NITROPARAFFINS IN IONIC MELTS
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It was shown that pure low-molecular nitroparaffins can be synthesized by the reaction between alkyl sodium sulfates and nitrite ion in ionic melts.The yield of the product is temperature controlled.Because of the ambident nature of nitrite ion, the main side product is alkyl nitrite, subsequent decomposition of which results in formation of a series of organic oxygen-containing compounds.The formal kinetics of the alkylation of nitrite ion by alkyl sodium sulfates was found to be described by the first-order equation.
- Belobrzhetskaya, M. K.,Laskin, B. M.,Malin, A. S.
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p. 105 - 108
(2007/10/02)
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- Tetraphenylphosphonium Nitrites
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Three different forms of tetraphenylphosphonium nitrite have been found to exist: an ionic nitrite, a co-ordinated nitrite, and a molecular species.
- Clark, James H.,Macquarrie, Duncan J.
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p. 229 - 230
(2007/10/02)
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- THE C-ALKYLATION OF NITROALKANE ANIONS BY 1-SUBSTITUTED-2-T-BUTYL-4-PHENYL- AND -2,4-DIPHENYL-5,6-DIHYDROBENZOQUINOLINIUM CATIONS.
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The N-substituents are transferred from the title cations to the C-atom of nitroalkane anions in high yield at 25-80 deg C in DMSO solution.The title cations are readily available from the appropriate pyrylium cations and primary amines of types RCH2NH2 and RR'CHNH2, allowing a general 2-step method for the preparation of higher nitroalkanes.Spectral properties of a variety of nitroalkanes are discussed.
- Katritzky, Alan R.,Kashmiri, M. Akram,Wittmann, Dieter K.
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p. 1501 - 1510
(2007/10/02)
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- The Synthesis of 1,4-Diketones via Fluoride-catalysed Michael Addition and Supported-permanganate-promoted Nef Transformation
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A versatile synthetic route for the preparation of 1,4-diketones from simple starting materials is described and applied to the preparation of a wide range of diketones.The two most important steps in the reaction are the fluoride ion-catalysed Michael addition of a nitroalkane to a vinyl ketone and the subsequent transformation of the nitro ketone to the diketone using supported permanganate as the oxidant.The interaction of F- with nitroethane has been studied and a number of sources of F- have been tested in the Michael addition reaction.Potassium fluoride supported on alumina and potassium permanganate supported on silica gel are remarkably efficient reagents for the Michael addition and Nef transformation stages, respectively, although it is important to determine the best reagent loadings and drying conditions for maximum reaction efficiency to be achieved.
- Clark, James H.,Cork, David G.,Gibbs, Hugh W.
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p. 2253 - 2258
(2007/10/02)
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- Desulphonylation of α-Nitrosulphones with N-Benzyl-1,4-dihydronicotinamide
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A sulphonyl group of α-nitrosulphones is replaced by hydrogen on treatment with N-benzyl-1,4-dihydronicotinamide; the reaction proceeds by a non-chain, free-radical process involving one-electron transfer.
- Ono, Noboru,Tamura, Rui,Tanikaga, Rikuhei,Kaji, Aritsune
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- Preparation of carboxylic acids from salts of nitroketones
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A method of preparing carboxylic acids is provided by contacting an ammonium, Group IA or Group IIA metal salt of a nitroketone in an aqueous medium. The method is preferably undertaken in the presence of an acidic mineral acid salt.
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