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E-factor minimized protocols for the polystyryl-BEMP catalyzed conjugate additions of various nucleophiles to alpha,beta-unsaturated carbonyl compounds

Efficient protocols for the addition of carbon-, sulphur- and nitrogen-nucleophiles to alpha,beta-unsaturated carbonyl compounds catalyzed by PS-BEMP have been reported. The adoption of solvent-free conditions (SolFC) was crucial for improving the efficiency of all the processes, while by using an organic reaction medium poor results were obtained. Addition reactions were performed by using equimolar amounts of reagents, and the products were isolated by simple filtration with the minimal amount of organic solvent. This approach allowed the E-factor, a measure of the waste of a reaction, to be minimized. Further waste minimization (95.7% compared to batch protocol) has been accomplished by defining a larger scale continuous-flow protocol operating under SolFC.

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Reference:
Oxazolidine – Wikipedia,
Oxazolidine | C3H358NO – PubChem

 

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Amine-salt-controlled, catalytic asymmetric conjugate addition of various amines and asymmetric protonation

Matrix presented. The combined use of chiral Pd complex 2 and amine salt enabled completely regulated release of free nucleophilic amine. Under these conditions, an efficient catalytic asymmetric conjugate addition of various amines was achieved to afford beta-amino acid derivatives in high chemical yields with up to 98% ee. Furthermore, a highly enantioselective protonation in 1,4-addition of amine was also developed.

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Oxazolidine – Wikipedia,
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Nickel-Copper-Catalyzed C(sp2)- N Cross-Coupling of Cyclic and Bridged Amides: An Access to Cyclic Enamides and Alkenyl Vince Lactams

An efficient C(sp2)- N cross-coupling of styrenyl and vinyl halides with cyclic and bridged amides catalyzed by nickel acetonylacetonate [Ni(acac)2] and copper(I) iodide (CuI) in the absence of any ligand has been developed. The reaction conditions are optimized to give the maximum yield of products using cesium carbonate (Cs2CO3) (2.0 equiv.) in N-methyl-2-pyrrolidinone (NMP) at 110 C under argon in the presence of Ni(acac)2/CuI (10 mol% each). A series of alkenyl derivatives of Vince lactams (bridged amides) and cyclic amides are obtained by this procedure. Halogen-containing styrenyl bromides also underwent coupling with amides to provide the products. The coupling is highly chemoselective as during the reactions the halogens (Br, Cl, F) on the aromatic ring remained intact and these can be used for further functionalization to make these enamides more useful. Although the (E)-styrenyl halides produced the corresponding (E)-styrenyl enamides, reactions with (Z)-styrenyl halides produced 1,3-di-ynes instead of (Z)-styrenyl enamides. This may be explained by the possibility of E2 type elimination of (Z)-styrenyl halides in the presence of a strong base like cesium carbonate followed by homocoupling. This catalyst system works efficiently for the N-arylation too along with N-styrenylation and vinylation. The bridged as well as cyclic amides successfully coupled with substituted aryl halides to provide the corresponding products. In general, the reactions are clean and high yielding. The operations are very simple and the products are obtained pure by standard column chromatography. The reaction is compatible with variety of amides and alkenyl bromides. The roles of nickel acetonylacetonate and copper(I) iodide in this reaction have been established and a possible reaction pathway has been outlined. The significant feature of this protocol is the alkenylation of Vince lactams via C(sp2)- N cross-coupling, which has not been reported so far and these products may have much potential in the pharmaceutical industry.

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Reference:
Oxazolidine – Wikipedia,
Oxazolidine | C3H785NO – PubChem

 

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Unusual aluminum hydride-mediated reduction of N-(gamma- or delta-oxoacyl)oxazolidinone

Reduction of N-(gamma-oxoacyl)oxazolidinone with a borohydride reagent, such as NaBH4 or LiBEt3H, resulted in formation of the corresponding lactone or lactol. In contrast, when an aluminum hydride reagent was used instead of a borohydride reagent, reduction of N-(gamma- or delta-oxoacyl)oxazolidinone proceeded unexpectedly to give not the corresponding lactone or lactol, but a tetrahydrofuran or tetrahydropyran derivative, respectively, containing an oxazolidino group.

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Oxazolidine – Wikipedia,
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New Copper(I)/DBU Catalyst System for the Carboxylative Cyclization of Propargylic Amines with Atmospheric CO2: An Experimental and Theoretical Study

Carbon dioxide (CO2) is an abundant and renewable feedstock for the production of high-value chemicals. Herein, CuI and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) were employed as an efficient catalyst system to synthesize 2-oxazolidinones through the coupling reaction of CO2 and propargylic amines. It was found that this cost-competitive catalyst system could efficiently catalyze the reaction within only 4 h at atmospheric pressure CO2, and a wide range of substrates were suitable for this reaction. Various target products were obtained in excellent yields. Furthermore, the catalytic mechanism of the CuI/DBU system was investigated by using density functional theory. It was shown that copper(I) and DBU played synergistic roles in activating both the C=C triple bond and the amino group of propargylic amines in the reaction.

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Oxazolidine – Wikipedia,
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LiOtBu Promoted 5-Exo?dig Cyclization of Propargyl Alcohols and Isocyanates for the Synthesis of Multisubstituted 3H-Oxazol-2-ones and Oxazolidin-2-ones

This study presents an efficient procedure for synthesis of 3,4,5-trisubstituted 3H-oxazol-2-ones and 3,4-disubstituted (Z)-oxazolidin-2-ones from substituted propargyl alcohols and aryl/alkyl isocyanates in the presence of LiOtBu, a base, and DMF, a solvent. This one-step, low-cost and gram scale synthesis exhibits superior atom economy, good to excellent yields, enhanced substrate scope and, high functional group tolerance and uses column chromatography-free purifications. Further, a product containing bromo substituent was successfully examined for Suzuki coupling with a view to amplifying the complexity of the molecule. Finally, the three component (aniline, Di-tert-butyldicarbonate and propargyl alcohol) reaction was demonstrated to get the oxazolon-2-ones (3H-oxazol-2-one and oxazolidin-2-one).

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Oxazolidine – Wikipedia,
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Synthesis of sterically hindered enamides via a Ti-mediated condensation of amides with aldehydes and ketones

The first TiCl4-mediated condensation of secondary amides with aldehydes and ketones has been achieved. The reaction proceeds at room temperature and is complete within 5 h in most cases. The optimized procedure used 5 equiv of an amine base hinting that the in situ activation of both the amide and the Lewis acid is required. The reaction affords polysubstituted (E)-enamides.

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Oxazolidine – Wikipedia,
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Hydrative Aminoxylation of Ynamides: One Reaction, Two Mechanisms

Organic synthesis boasts a wide array of reactions involving either radical species or ionic intermediates. The combination of radical and polar species, however, has not been explored to a comparable extent. Herein we present the hydrative aminoxylation of ynamides, a reaction which can proceed by either a polar-radical crossover mechanism or through a rare cationic activation. Common to both processes is the versatility of the persistent radical TEMPO and its oxidised oxoammonium derivative TEMPO+. The unique mechanisms of these processes are elucidated experimentally and by in-depth DFT-calculations.

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Oxazolidine – Wikipedia,
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Br°nsted Acid-Catalyzed Cyclization of beta-Amino-1,4-enols to Oxazol-2(3H)-ones and 5-Alkenyloxazolidin-2-ones

A synthetic method to prepare oxazol-2(3H)-ones and 5-alkenyloxazolidin-2-ones efficiently that relies on a Br°nsted acid-catalyzed cyclization of the respective secondary and tertiary beta-amino-1,4-enols in ethanol is described. The reaction did not require the exclusion of air or moisture.

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Oxazolidine – Wikipedia,
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A general, facile, and safe procedure for the preparation of S-methyl N-alkylthiocarbamates by methylthiocarbonylation of primary aliphatic amines with S,S-dimethyl dithiocarbonate

A general procedure is reported for the selective preparation of S-methyl N-alkylthiocarbamates by methylthiocarbonylation of primary aliphatic amines, employing S,S-dimethyl dithiocarbonate as a phosgene substitute. The reactions are carried out in water at room temperature (20-25C), with S,S-dimethyl dithiocarbonate/amine ratios varying between 1:1.2 and 1:2, and with quantitative recovery of the excess amine. The target products are obtained in exceptionally high yields (generally >95%) and with very high purity (generally >99.5%). Also to be noted is the complete chemoselectivity of the reactions, which can be carried out in the presence of hydroxy or aminophenyl groups. Georg Thieme Verlag Stuttgart.

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Reference:
Oxazolidine – Wikipedia,
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