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Electrogenerated N-heterocyclic carbene: N-acylation of chiral oxazolidin-2-ones in ionic liquids

An electrochemical procedure for the N-acylation of chiral oxazolidin-2-ones, in the absence of volatile molecular organic solvents, has been set up via electrolyses of ionic liquid [bmim]BF4 containing oxazolidin-2-ones followed by addition of saturated or unsaturated anhydrides. N-acyloxazolidin-2-ones were isolated in good to elevated yields. The electrochemically induced N-acylation of chiral oxazolidin-2-ones occurs with total retention of the absolute configuration of all the chiral atoms. The electrogenerated carbene (1-butyl-3-methyl-1H-imidazol-2-ylidene) has been indicated as the base involved in the deprotonation of chiral oxazolidin-2-ones.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H2237NO – PubChem

 

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Asymmetric synthesis of beta-amino acids by addition of chiral enolates to nitrones via N-acyloxyiminium ions

N-Acyloxyiminium ions, generated by the reaction of nitrones with acyl halides, are highly reactive species and undergo facile reaction with a wide range of nucleophiles, such as ketene silyl acetals, titanium(IV) and boron enolates, hydrido- and allyltin(IV) reagents, and alkynyltitanium(IV) reagents, to give alpha-substituted amine derivatives. Optically active beta-amino acids can be prepared by the reaction of N-acyloxyiminium ions with both boron and titanium(IV) enolates bearing chiral auxiliaries. Reversal of diastereoselectivity was observed by the reactions of the boron and titanium(IV) enolates. Using these reactions, all of the four stereoisomers of alpha-methyl-beta-phenylalanines, for example, can be prepared highly diastereoselectively. Cyclic N-acyloxyiminium ions are useful for the asymmetric synthesis of pyrrolidine and piperidine alkaloids; (5R,8R,8aS)-5-cyano-8-methylindolizidine, which is a common key intermediate for synthesis of 5-substituted 8-methylindolizidines, was prepared selectively.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H2243NO – PubChem

 

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One Pot Synthesis of N-Derivatized 2-Oxazolidinones from Amino Alcohol Carbamates

A one pot protocol for the synthesis of N-derivatized 2-oxazolidinones from amino alcohol carbamates is described.The method is exceptionally useful if the parent amino acids are prepared in their enantiopure forms via enzymatic resolution of the racemic carbamate esters.

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An Activated Germanium Metal-Promoted, Highly Diastereoselective Reformatsky Reaction

Activated germanium metal, prepared by the reduction of germanium(II) iodide with potassium metal, was found to promote the Reformatsky reaction effectively under mild conditions. In the presence of activated germanium metal, the reactions of alpha-bromo ketones 2a and 2b and alpha-bromo imides 2e and 2f with benzaldehyde (1a) proceeded smoothly to give the corresponding beta-hydroxy carbonyl compounds 3a, 3b, 3e and 3f, respectively, in good yields and with good syn diastereo- selectivity. The activated germanium metal-promoted, asymmetric Reformatsky reaction of enantiomerically pure-oxazolidinone derivatives 2g-j with various aldehydes 1a-d was also examined; the highest diastereoselectivity was achieved when (1S,2R)-2-amino-1,2-diphenylethanol- derived 2j was used as the Reformatsky donor. The excellent diastereoselectivity could be explained in terms of the formation of a chairlike, six-membered transition state between the aldehyde and enolate as in the Zimmerman-Traxler model. A single recrystallization of the Reformatsky adducts, followed by hydrolysis and subsequent esterification, led to enantiomerically pure methyl 3-hydroxy- 2-methylalkanoates 10j-m, with almost quantitative recovery of the enantiomerically pure 2-oxazolidinone 14.

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Oxazolidine – Wikipedia,
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Concise synthesis of the C-1-C-12 fragment of amphidinolides T1-T5

The C-1-C-12 segment of the amphidinolides T1-T5 has been synthesised in an efficient manner. The key transformations are highly diastereoselective rearrangement of an oxonium ylide, or metal-bound ylide equivalent, produced by intramolecular reaction of a copper carbenoid with an allylic ether, and macrocyclic fragment coupling by one-pot ring-closing metathesis and hydrogenation. The Royal Society of Chemistry 2011.

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Oxazolidine – Wikipedia,
Oxazolidine | C3H2238NO – PubChem

 

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Diastereoselective Electrochemical Carboxylation of Chiral alpha-Bromocarboxylic Acid Derivatives: An Easy Access to Unsymmetrical Alkylmalonic Ester Derivatives

The diastereoselective electrochemical carboxylation of chiral N-(2-bromoacyl)oxazolidin-2-ones has been studied. This reaction was carried out by cathodic reduction of the C – Br bond, in the presence of carbon dioxide, followed by treatment with diazomethane. The yields and the diastereomeric ratio of the two epimeric alkylmalonic acid derivatives are strongly affected by various factors: solvent-supporting electrolyte system, temperature, electrode material, electrolysis conditions, oxazolidinone moiety. The higher yields (88%) were obtained starting from N-(2-bromopropionyl)-4R-phenyloxazolidin-2-one la, but with poor diastereoselectivity (61:39). The two epimers were easily separated by flash chromatography. The best results were achieved using a different chiral auxiliary: Oppolzer’s camphor sultam. Starting from 1j a good yield in carboxylated product was obtained (80%) with excellent diastereoselectivity (98:2). These chiral alkylmalonic acid derivatives are valuable building blocks in the synthesis of molecules with biological activity and of chiral propane-1,3-diols derivatives.

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Kinetic resolution of 2-oxazolidinones via catalytic, enantioselective N-acylation

Kinetic resolution of racemic 2-oxazolidinones via catalytic, enantioselective N-acylation has been achieved for the first time and with outstanding selectivities. Copyright

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Oxazolidine – Wikipedia,
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Diastereoselective Electrophilic Trifluoromethylthiolation of Chiral Oxazolidinones: Access to Enantiopure alpha-SCF3 Alcohols

Lithium imide enolates featuring Evans? chiral oxazolidinone auxiliary were involved in diastereoselective alpha-trifluoromethylthiolation with electrophilic SCF3 donors. Diastereopure products were isolated and converted to enantiopure alpha-SCF3 alcohols without racemisation. (Figure presented.).

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Oxazolidine – Wikipedia,
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An electrophilic hypervalent iodine reagent for trifluoromethylthiolation

Sulfur and friends: A new electrophilic hypervalent iodine reagent 1 has been developed for direct trifluoromethylthiolation. A variety of nucleophiles, including beta-ketoesters, aldehydes, amides, aryl or vinyl boronic acids, and alkynes, reacted with 1 under mild conditions to give the corresponding trifluoromethylthiolated compounds in good to excellent yields.

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160695-26-1, (R)-4-Phenyl-3-propionyloxazolidin-2-one is a oxazolidine compound, ?involved in a variety of chemical synthesis. Rlated chemical reaction is continuously updated

Preparation Example 2-1: (S)-t-butyl 2-((1R,2R)-1-hydroxy-2-methyl-3-oxo-3-((R)-2-oxo-4-phenyloxazolidin-3-yl)propyl)pyrrolidine-1-carboxylate (VI-1) [0060] [0061] To a solution of (R)-4-phenyl-3-propionyloxazolidin-2-one (605 mg, 2.7 mmol) in 8 mL of dichloromethane that was cooled to 0C, triethyl amine (0.5 mL, 3.7 mmol) was added. Then, dibutylboron triflate was added dropwise and stirred drops of dibutylboron triflate were added before stirring for 45 min. The resulting solution was cooled to -78C, added dropwise of a solution of the compound (IV-1) (500 mg, 2.5 mmol), obtained in Preparation Example 1-1, in 5 mL of dichloromethane, and stirred for 1 hr. Stirring was further conducted at 0C for an additional 1 hr, and at 20?25C for an additional 1 hr. [0062] The reaction was terminated with a phosphate buffer (pH 7.2, 3 mL) and 9 mL of methanol. The reaction mixture was cooled to 0C before a mixture of methanol: 33% hydrogen peroxide (2 : 1, 9 mL) was dropwise added thereto. It was stirred for 1 hr, and concentrated in a vacuum. The concentrate was dissolved in ether, washed with saturated sodium chloride, dried over anhydrous sodium sulfate, and concentrated in a vacuum to give a yellow oil. Recrystallization in ethyl acetate afforded the title compound as a white solid. 0.59 g (59%). MS (EI) m/z : 419 [M+H]+ 1H NMR (400 MHz, CDCl3): delta 1.10 (m, 3H), 1.39 (s, 9H), 1.67?1.84 (m, 7H), 3.01 (m, 1H), 3.67?3.81 (m, 3H), 4.14 (m, 1H), 4.70 (m, 1H), 5.03 (m, 1H), 5.43 (m, 1H), 7.26?7.41 (m, 5H)

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Reference£º
Patent; Celltrion, Inc.; PARK, Young Jun; JEONG, Jin-kyo; CHOI, Young Mi; LEE, Min Seob; CHOI, Joon hun; CHO, Eun Joo; SONG, Hyunnam; PARK, Sung Jun; LEE, Jong-hyoup; HONG, Seung Suh; EP2889287; (2015); A1;,
Oxazolidine – Wikipedia
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