Regiochemical control of the ring opening of 1,2-epoxides by means of chelating processes. 5. Synthesis and reactions of some 2,3-epoxy-1-alkanol derivatives

Chini, Marco; Crotti, Paolo; Flippin, Lee A.; Gardelli, Cristina; Giovani, E.; Macchia, Franco; Pineschi, Mauro

doi:10.1021/jo00057a040

Cited by 94 publications

(40 citation statements)

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“…The nitrile group present in 5 was reduced to a hydroxymethyl substituent in two steps, first treatment with DIBALH at À 78 8C produced the intermediate aldehyde, and subsequently reaction with sodium borohydride in ethanol at room temperature gave epoxy alcohol 3 (Scheme 2). Ring opening of 3 proceeded smoothly in quantitative yield using a modified procedure of the method described by Crotti, [8] and already used for the preparation of 1 from triphenylethylene oxide. Following this reaction sequence, aminodiol 2 ready for anchoring, can be obtained from enantiopure epoxide 5 in three steps with 76% overall yield.…”

Section: Resultsmentioning

confidence: 99%

Tail‐Tied Ligands: An Immobilized Analogue of (R)‐2‐Piperidino‐1,1,2‐triphenylethanol with Intact High Catalytic Activity and Enantioselectivity

et al. 2003

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A functional analogue of (R)-2-piperidino-1,1,2-triphenylethanol was synthesized and anchored to different polymeric supports by a position remote from the active region. This strategy, leading to what we call a tail-tied ligand, allows for the achievement of the optimal transition state geometry in the catalytic process. The catalytic activity of the resulting heterogenized ligands was investigated by online FTIR analysis. The optimum polymer was assayed in the addition reaction of diethylzinc to a large family of aldehydes rendering essentially intact high catalytic activity and enantioselectivity compared to its homogeneous counterpart.

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Section: Resultsmentioning

confidence: 99%

Tail‐Tied Ligands: An Immobilized Analogue of (R)‐2‐Piperidino‐1,1,2‐triphenylethanol with Intact High Catalytic Activity and Enantioselectivity

et al. 2003

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“…4). Previous studies have shown that both epoxide and carbonyl groups add amines (26,27). ESI-MS/MS analysis of the fatty acid isolated from m/z 810.5 (i2) (Fig.…”

Section: Discussionmentioning

confidence: 98%

Structural Identification of a Novel Pro-inflammatory Epoxyisoprostane Phospholipid in Mildly Oxidized Low Density Lipoprotein

Watson¹,

Subbanagounder²,

Welsbie³

et al. 1999

Journal of Biological Chemistry

207

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One of the earliest steps in the development of the atherosclerotic lesion is the accumulation of monocyte/ macrophages within the vessel wall. Oxidized lipids present in minimally modified-low density lipoproteins (MM-LDL) contribute to this process by activating endothelial cells to express monocyte-specific adhesion molecules and chemoattractant factors. A major focus of our group has been the isolation and characterization of the biologically active oxidized lipids in MM-LDL. We have previously characterized three oxidized phospholipids present in MM-LDL, atherosclerotic lesions of fat fed rabbits, and autoxidized 1-palmitoyl-2-arachidonoyl-snglycero-3-phosphocholine (Ox-PAPC) that induced human aortic endothelial cells to adhere human monocytes in vitro. We have used sequential normal and reverse phase-high performance liquid chromatography to isolate various isomers of an oxidized phospholipid from autoxidized 1-palmitoyl-2-arachidonoyl-sn-glycero-3-phosphocholine. The fatty acid in the sn-2 position of this biologically active isomer and its dehydration product was released by phospholipase A 2 and characterized. Hydrogenation with platinum(IV) oxide/hydrogen suggested a cyclic moiety, and reduction with sodium borohydride suggested two reducible oxygencontaining groups in the molecule. The fragmentation pattern produced by electrospray ionization-collision induced dissociation-tandem mass spectrometry was consistent with a molecule resembling an E-ring prostaglandin with an epoxide at the 5,6 position. The structure of this lipid was confirmed by proton nuclear magnetic resonance spectroscopy analysis of the free fatty acid isolated from the dehydration product of m/z 828.5. Based on these studies, we arrived at the structure of the biologically active oxidized phospholipids as 1-palmitoyl-2-(5,6-epoxyisoprostane E 2 )-sn-glycero-3-phosphocholine. The identification of this molecule adds epoxyisoprostanes to the growing list of biologically active isoprostanes.

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“…Compounds 11 b and 11 f were obtained by regioand stereospecific hydroxyselenation of the corresponding allylic ethers [30] using phenylselenyl chloride. [31] Compound 6 l was prepared by acidic hydrolysis of the corresponding oxazoline, [32] while 6 g was obtained by alkaline hydrolysis and subsequent esterification of the corresponding lactone with diazomethane [32] .…”

Section: Methodsmentioning

confidence: 99%

Ring‐Closure Reactions through Intramolecular Displacement of the Phenylselenonyl Group by Nitrogen Nucleophiles: A New Stereospecific Synthesis of N‐Tosyl and N‐Benzoyl‐1,3‐oxazolidin‐2‐ones from β‐Hydroxyalkyl Phenyl Selenides

Tiecco

Testaferri

Temperini

et al. 2004

Chemistry A European J

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A new and convenient method for the stereospecific synthesis of variously substituted 1,3-oxazolidin-2-ones from the easily available beta-hydroxyalkyl phenyl selenides is presented. After transformation into the N-tosyl or N-benzoyl carbamates, the selenides were oxidized to the corresponding selenones. The key step of the process is the ring-closure reaction, which occurs by stereospecific intramolecular nucleophilic substitution of the selenone group by the nitrogen atom of the carbamate. Enantiomerically pure 1,3-oxazolidin-2-one derivatives can be easily prepared by using enantiomerically pure beta-hydroxyalkyl phenyl selenides as starting materials.

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Regiochemical control of the ring opening of 1,2-epoxides by means of chelating processes. 5. Synthesis and reactions of some 2,3-epoxy-1-alkanol derivatives

Cited by 94 publications

References 0 publications

Tail‐Tied Ligands: An Immobilized Analogue of (R)‐2‐Piperidino‐1,1,2‐triphenylethanol with Intact High Catalytic Activity and Enantioselectivity

Tail‐Tied Ligands: An Immobilized Analogue of (R)‐2‐Piperidino‐1,1,2‐triphenylethanol with Intact High Catalytic Activity and Enantioselectivity

Structural Identification of a Novel Pro-inflammatory Epoxyisoprostane Phospholipid in Mildly Oxidized Low Density Lipoprotein

Ring‐Closure Reactions through Intramolecular Displacement of the Phenylselenonyl Group by Nitrogen Nucleophiles: A New Stereospecific Synthesis of N‐Tosyl and N‐Benzoyl‐1,3‐oxazolidin‐2‐ones from β‐Hydroxyalkyl Phenyl Selenides

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