91957-34-5

Upstream product

• 128457-29-4 3-benzyl-4-hydroxy-4,5,5-trimethyl-2-oxazolidinone 
• 115-19-5 2-methyl-but-3-yn-2-ol 
• 100-46-9 benzylamine 
• 73818-55-0 Bestmann ylide 
• 103853-77-6 2-hydroxy-2-methyl-N-benzylpropanamide 
• 124-38-9 carbon dioxide 
• 937021-08-4 benzylcarbamic acid 1,1-dimethylprop-2-ynyl ester 
• 4437-80-3 4,4-dimethyl-5-methylene-1,3-dioxolan-2-one 

Relevant academic research and scientific papers

Upgrading CO2 by Incorporation into Urethanes through Silver-Catalyzed One-Pot Stepwise Amidation Reaction

One-pot two-step stepwise reaction of terminal propargylic alcohols, carbon dioxide, and primary/secondary amines for the effective synthesis of various urethanes through robust silver-catalysed C-O/C-N bond formation is reported. Catalytic activities were investigated by controlling catalyst loading, reaction pressure and time, and very high turnover number (turnover frequency) was obtained: 3350 (35 h?1) with 0.01 mol% silver catalyst under 0.1 MPa, and up to 13360 (139 h?1) with 0.005 mol% silver catalyst under 2.0 MPa at room temperature. The strategy was ingeniously regulated, and synchronously afforded a wide range of β-oxopropylcarbamate and 1,3-oxazolidin-2-one motifs in excellent yields and selectivity together with unprecedented high turnover number (TON) and turnover frequency (TOF) value.

4 - methylene - 2 - oxazolidinone preparation method

The invention discloses a method for preparing 4-methylene-2-oxazolidinone. The method comprises the following step: in the presence of a compound shown in a formula IV, performing cyclization reaction on a compound shown in a formula II and a compound shown in a formula III under the carbon dioxide atmosphere to obtain the compound shown in a formula I. A non-metal organic molecule terpyridyl is taken as a catalyst system so that the target product pollution caused by the metal ion due to the use of the metal catalyst can be effectively avoided and the pharmaceutical synthesis requirement of the target product is guaranteed. The catalyst is simple in system, cheap, high in activity, stable in performance and easy to separate and recycle and is environmentally friendly and the production cost is saved; furthermore, the cyclization reaction is a non-solvent system so that the cost is additionally saved. The formulae are as shown in the specification.

Au-Catalyzed [2 + 3] Annulation of Enamides with Propargyl Esters: Total Synthesis of Cephalotaxine and Cephalezomine H

A novel Au-catalyzed [2 + 3] annulation reaction of enamides with propargyl esters has been developed, providing a new method for expeditious assembly of synthetically useful functionalized 1-azaspiro[4.4]nonane building blocks. Based on this key annulation, strategic installation of the pivotal azaspirocyclic core, followed by constructing the benzazepine unit via Witkop cyclization, led to the divergent total syntheses of cephalotaxine and cephalezomine H.

Conversion of carbon dioxide into 2-oxazolidinones and 2(3H)-oxazolones catalyzed by 2,2′,2″-terpyridine

The catalytic activation of pyridines as organocatalysts in the three-component cycloaddition of CO2, propargyl alcohol and primary amine was investigated, and 2,2′,2″-Terpyridine was found to be the efficient organocatalyst to afford 4-methylene-2-oxazolidinones or 2(3H)-oxazolones in good to high yields. 2,2′,2″-Terpyridine also showed high catalytic activity in the coupling reaction of CO2 with aziridines bearing either electron-donating or electron-withdrawing N-substituents to give substituted 2-oxazolidinones in high yields.

Efficient chemical fixation of CO2 promoted by a bifunctional Ag2WO4/Ph3P system

An efficient heterogeneous silver-catalyzed reaction for construction of the α-methylene cyclic carbonate motif was developed through carboxylative assembly of propargyl alcohols and CO2. Such a CO2 fixation protocol proceeded smoothly with only 1 mol% of Ag2WO 4 and 2 mol% of PPh3 as well as atmospheric CO2 at room temperature under solvent-free conditions, in an environmentally benign and low energy manner along with an easy operating procedure. Notably, up to 98% isolated yields of carbonates could be attained with exclusive chemo-selectivity. In addition, the dual activation capacity of Ag 2WO4 towards both the propargylic substrate and CO 2 is based on which cooperative catalytic mechanism by the silver cation and the tungstate anion is proposed. Recycling trials on carboxylative cyclization of propargyl alcohols and CO2 illustrate that the catalyst can be reused at least 4 times with retention of high catalytic activity and selectivity. Especially, it allows the direct and effective application in the one-pot synthesis of various oxazolidinones bearing exocyclic alkenes and carbamates in moderate to high yields upon the alternative introduction of primary or secondary amines.

Effective guanidine-catalyzed synthesis of carbonate and carbamate derivatives from propargyl alcohols in supercritical carbon dioxide

The reactions of propargyl alcohols with carbon dioxide in supercritical carbon dioxide or in acetonitrile with gaseous carbon dioxide in the presence of organic bases as catalysts have been examined. Bicyclic guanidines are effective catalysts for the formation of α-methylene cyclic carbonates under mild reaction conditions. Oxoalkyl carbonates, oxoalkyl carbamates or α-methyleneoxazolidinones are obtained in high yields and good selectivities in one-step starting from propargyl alcohols and an external nucleophile (alcohols or amines) using bicyclic guanidines as catalysts in supercritical carbon dioxide. Propargylic diols under the same reaction conditions underwent a rearrangement process instead of carbon dioxide insertion whereas in the presence of an external nucleophile the formation of oxocarbonates, oxocarbamates or cyclic carbamates was achieved in satisfactory yields.

Efficient and eco-friendly process for the synthesis of N-substituted 4-methylene-2-oxazolidinones in ionic liquids

The carbonylation of amines with propargylic alcohol using CO2 as carbonyl source to yield N-substituted 4-methylene-2-oxazolidinones could efficiently proceed in ionic liquids, and various 4-methylene oxazolidinones with high yields could be obtained under relatively mild conditions. This result showed that ionic liquid might be an effective catalyst and reaction medium for the activation of CO2, which also offered a new way to the chemical fixation of CO2.

Reactions of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with amines in the presence of palladium catalyst

In the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with primary amines in the presence of Pd(0) catalyst, the 3-alkyl-4-hydroxy-4,5,5-trimethyloxazolidin-2-ones (1) are obtained as the major products, along with the formation of ring opened products at room temperature. On the other hand, 3-alkyl-5,5-dimethyl-4-methyloxazolidin-2-ones (2) are obtained as reaction products in high yields at high temperature. But in the absence of Pd(0) catalyst, the ring opened compounds alkylcarbamic acid 1,1-dimethyl-2-oxopropyl esters (3) are formed exclusively. In addition, in the reaction of 5,5-dimethyl-4-methylene-1,3-dioxolan-2-one with secondary amines, the ring opened compounds were obtained as the sole products. A plausible mechanism for the formation of 1 and 2 is proposed.

2(3H)-oxazolones from α-hydroxy amides and keteneylidenetriphenylphosphorane via a phoshorus ylide cascade

Upon heating in xylene α-hydroxyamides 3 react with the cumulated phosphorus ylide 1 to give the substituted 2(3H)-oxazolones 8 in 40-80% yield. The reaction proceeds via an addition/cyclization/intermolecular-Wittig olefination sequence, which implies th

A simple synthesis of oxazolidinones in one step from carbon dioxide

The reaction of carbon dioxide, propargyl alcohol derivatives and primary amines, catalysed by phosphine, gives N-substituted 4-methylene-oxazolidin-2-ones.