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Highly efficient phosphine-catalyzed aza-Michael reactions of alpha,beta-unsaturated compounds with carbamates in the presence of TMSCl

Aza-Michael reactions of enones with carbamates took place efficiently in the presence of a catalytic amount of phosphine and TMSCl to afford the total products in high yields. The new catalytic system was also efficient in the aza-Michael reaction of chalcone, which was difficult to react with carbamates by transition metal salts catalysts.

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Reference:
Oxazolidine – Wikipedia,
Oxazolidine | C3H1154NO – PubChem

 

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Divergent selectivity in Mgl2-mediated ring expansions of methylenecyclopropyl amides and imides

We report a novel approach to prepare five- and six-membered heterocyclic compounds via a ring expansion of monoactivated methylenecyclopropanes (MCPs) with aldimines and aldehydes in the presence of MgI2. Monoactivated MCPs behave as homo-Michael acceptors to afford bifunctional vinylogous enolates in the presence of MgI2. The carbonyl moiety of the monoactivated MCP dramatically influences the reaction site in the dienolate with aryl aldimines and aldehydes as well as the size of the ring. Excellent divergent selectivity to five- vs. six-membered heterocycles is observed: alpha-alkylation/5-exo-tet cyclization (Z = NPh2) vs. gamma-alkylation/6-exo- trig cyclization (Z = 2-oxazolidone). Analogously, the reaction of the MCP imide with alkyl aldimines demonstrates the same selectivity by varing the size of electrophile or the reaction temperature. In addition, we observe the first example of the formation of the gamma-alkylation adduct in the reaction of a vinylogous imide enolate with a carbonyl compound.

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Reference:
Oxazolidine – Wikipedia,
Oxazolidine | C3H721NO – PubChem

 

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A highly efficient sulfur-catalyzed oxidative carbonylation of primary amines and beta-amino alcohols

A highly efficient sulfur-catalyzed oxidative carbonylation of aliphatic amines and aliphatic beta-amino alcohols to ureas and 2-oxazolidinones, respectively, was developed. Sodium nitrite was involved in the reoxidation of hydrogen sulfide to sulfur in the catalytic oxidative carbonylation cycle. Georg Thieme Verlag Stuttgart.

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Oxazolidine – Wikipedia,
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NOVEL CYCLIC HYDROCARBON COMPOUNDS FOR THE TREATMENT OF DISEASES

The invention relates to novel cyclic hydrocarbon compounds and derivatives thereof, processes for the preparation thereof, to said compounds for use as a medicament, to said compounds for use in therapy, to pharmaceutical compositions comprising said compounds, to methods of treating diseases with said compounds, and to the use of said compounds in the manufacture of medicaments.

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Oxazolidine – Wikipedia,
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Efficient and Divergent Synthesis of alpha-Halogenated Amides and Esters by Double Electrophilic Activation of Ynamides

An efficient and modular entry to alpha-halogenated amides and esters is reported. This reaction is based on an underestimated double electrophilic activation of ynamides sequentially involving highly reactive activated keteniminium and iminium ions. Upon simple reaction with HCl and an electrophilic halogenation reagent in the presence of water or an alcohol, a broad range of ynamides can be transformed, in a highly divergent manner, to alpha-halo amides and esters with high efficiency and under mild conditions.

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Oxazolidine – Wikipedia,
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Highly exo-selective and enantioselective cycloaddition reactions of nitrones catalyzed by a chiral binaphthyldiimine-Ni(II) complex

(Chemical Equation Presented) Significant levels of exo-selectivity (exo:endo = >99:1 to 86:14) and enantioselectivity (95-82% ee) were obtained in the 1,3-dipolar cycloadditions of a number of nitrones with 3-(2-alkenoyl)-2-thiazolidinethiones, using the chiral binaphthyldiimine-Ni(II) complex (5-20 mol %), which was easily prepared form N,N?-bis(3,5- dichrolo-2-hydroxybenzylidene)-1,1?-binaphthyl-2,2?-diamine and Ni(ClO4)2·6H2O in CHCl3 in the presence of 4 A molecular sieves, as a chiral Lewis acid catalyst.

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Reference:
Oxazolidine – Wikipedia,
Oxazolidine | C3H1029NO – PubChem

 

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Azides. Part VIII. Thermolysis of ethyl azidoformate in acetic and propionic anhydrides: facilitation of intramolecular cyclization of the resultant carbethoxynitrene to 2-oxazolidinone

The thermolysis of ethyl azidoformate in acetic and propionic anhydrides as solvent yielded the corresponding N-acyl-2-oxazolidinones (2a,b) in relatively significant yields.The other major products isolated were N-carboxyethyl-N,O-diacyl hydroxylamine (1a.b) and N,N,O-triacetyl hydroxylamine (3).The intramolecular cyclization is facilitated by the solvent.

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Oxazolidine – Wikipedia,
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Nitroimidazoles: Part XVI – Some 1-Methyl-4-nitro-5-substituted Imidazoles

Treatment of 1-methyl-4-nitro-5-chloroimidazole (3) with 5-membered lactames, e.g. imidazolidinones, oxazolidinone and thiazolidinone affords N-imidazolyl derivatives (4a-d).Reaction of 3 with imidazole yields 4e; amino derivatives (4f-h) are similarly obtained. 2-Hydroxypyrazine, 4-hydroxyquinazoline and 3,4,5-trichlorophenol and 3 react to form O-derivatives (4i-k).Imidazole (11) is formed from 1-methyl-4-chloro-5-nitroimidazole (10).

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Oxazolidine – Wikipedia,
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Synthesis of allenamides by Pd-catalyzed coupling of 3-alkoxycarbonyloxy ynamides or 1-alkoxycarbonyloxy allenamides with arylboronic acids

An efficient palladium-catalyzed method is reported for the synthesis of multi-substituted allenamides by Suzuki-Miyaura cross-coupling reaction between easily prepared 3-alkoxycarbonyloxy ynamides or 1-alkoxycarbonyloxy allenamides and arylboronic acids. The Royal Society of Chemistry 2012.

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Oxazolidine – Wikipedia,
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AgOTf-catalyzed reaction of sulfonyl hydrazones with ynamides led to stereoselective synthesis of alpha-amino alkenyl-substituted hydrazone derivatives

A novel method for the synthesis of alpha-amino alkenyl-substituted hydrazone derivatives was disclosed through silver-catalyzed reaction of sulfonyl hydrazones with ynamides. The present method features mild conditions, high stereoselectivity and good yields. The proposed mechanism involves silver-mediated generation of a keteniminium ion intermediate to facilitate the stereoselective addition of hydrazones in the presence of K2CO3, while pyrazole ring could not be constructed under the current conditions.

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Reference:
Oxazolidine – Wikipedia,
Oxazolidine | C3H397NO – PubChem