888329-89-3

Upstream product

• 90719-32-7 (S)-4-Benzyl-2-oxazolidinone 
• 932-87-6 1-Bromo-2-phenylacetylene 
• 536-74-3 phenylacetylene 

Downstream Products

• 1187370-57-5 (S,E)-4-benzyl-3-(1-(3-nitrophenylimino)-2-phenylethyl)oxazolidin-2-one 
• 104266-89-9 (S)-4-benzyl-3-phenylacetyl-2-oxazolidinone 
• 1448432-19-6 (S,Z)-4-benzyl-3-(2-phenylprop-1-en-1-yl)oxazolidin-2-one 
• 1538615-05-2 (4S)-4-benzyl-3-[(2S)-2,3-diphenylpropanoyl]-1,3-oxazolidin-2-one 
• 1617518-91-8 (S)-4-benzyl-3-[(Z)-1-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-2-phenyl-ethenyl]oxazolidin-2-one 

Relevant academic research and scientific papers

Highly regio- and stereocontrolled synthesis of β-substituted α-tributylstannyl enamides

The regio- and stereocontrolled synthesis of β-substituted α-stannyl enamides is reported starting from internal ynamides. The synthesis of new ynamides as well as bis-ynamides is also described. Finally first examples of successful cross-coupling to afford α/β-disubstituted enamides are also reported.

A Unified Approach for Divergent Synthesis of Heterocycles via TMSOTf-Catalyzed Formal [3+2] Cycloaddition of Electron-Rich Alkynes

We present a synthetic protocol for the construction of polysubstituted five-membered heterocycles via TMSOTf-catalyzed formal [3+2] cycloaddition of electron-rich alkynes, which features free from any metal, atom economy and water as the main by-product. Furthermore, alkenyl ether adduct has been verified as the key intermediate. Notably, by utilizing this approach, we can synthesize a broad range of polysubstituted furans, thiophenes and pyrroles, and extend this transformation to deliver fused-polyheterocycles. This reaction can be achieved on a gram scale and the corresponding products are intermediates for producing diverse potentially useful scaffolds. (Figure presented.).

Visible-Light-Promoted Oxo-Sulfonylation of Ynamides with Sulfonic Acids

A visible-light-promoted oxo-sulfonylation of ynamides with sulfonic acids is reported, giving rise to a collection of functionalized α-sulfonylated amides in a straightforward manner. The reaction proceeds sequentially through a cascade of electrophilic addition and photoinduced sulfonyl radical-sustained skeleton rearrangement. The high atom economy, mild reaction conditions, and wide substrate scope comprised the merits of this synthetic transformation.

Palladium-Catalyzed Oxygenative Cross-Coupling of Ynamides and Benzyl Bromides by Carbene Migratory Insertion

A palladium-catalyzed oxygenative cross-coupling of ynamides and benzyl bromides has been developed. After subsequent hydrogenation, α,α-disubstituted amide derivatives were obtained in good yields. Migratory insertion of α-oxo palladium carbene species, generated by intermolecular oxidation, is proposed as the key step in this reaction. The study demonstrates the potential of ynamides to serve as carbene precursors in palladium-catalyzed C?C bond-forming cross-coupling reactions.

Regioselective TfOH-mediated hydroamidation of ynamides with nitriles

A new TfOH-mediated reaction of ynamides with nitriles as nucleophiles has been developed. The reaction works efficiently under mild reaction conditions to afford a new class of α-acylaminoenamides readily via the intermediacy of keteniminium ion. The reaction displays generality and a broad substrates scope. Additionally, the α-acylaminoenamides could be transformed to highly substituted pyridine, 4-aminopyrimidine or isoquinoline cores.

Iridium-Catalyzed Highly Regioselective Azide-Ynamide Cycloaddition to Access 5-Amido Fully Substituted 1,2,3-Triazoles under Mild, Air, Aqueous, and Bioorthogonal Conditions

A highly regioselective method to access 5-amido fully substituted 1,2,3-triazoles by iridium-catalyzed azide-ynamide cycloaddition under mild, air, aqueous, and bioorthogonal conditions is reported. The excellent regioselectivities may derive from the strong coordination between the carbonyl oxygen of ynamide and the -acidic iridium. Since the iridium ion is insensitive to oxygen/water and exhibits low cytotoxicity, it could catalyze this reaction in both organic and biological environments efficiently. Preparation in gram-scale and application in carbohydrates highlight this method.

Multistereocenter-Containing Cyclopentanoids from Ynamides via Oxazolidinone-Controlled Nazarov Cyclization

Achieving ready-enantioselective access to multistereocenter-containing cyclopentyl rings is an area of great significance to organic synthesis. In this work, we describe a general protocol for accessing multistereocenter-containing cyclopentanoids from simple N-alkynyloxazolidinones (Ox-ynamides). This protocol involves conversion of Ox-ynamides into Ox-activated divinyl and aryl vinyl ketones that undergo facile Nazarov cyclization with excellent chemo-, regio-, and stereocontrol. The Ox auxiliary directs all aspects of reactivity and selectivity, both in the electrocyclization and in the subsequent transformations of the resulting oxyallyl intermediate. Stereoinduction in the electrocyclization results from a "coupled-torque" mechanism in which rotation of the Ox group, driven by increasing orbital overlap of the nitrogen lone pair with the incipient oxyallyl cation, is coupled with the rotation of the termini of the pentadienyl cation, favoring a particular direction of conrotatory ring closure (torquoselectivity). The associated lone-pair stabilization of the transition state by Ox promotes cyclization of traditionally resistant substrates, broadening the scope of this asymmetric Nazarov cyclization. The Ox group also facilitates the stereo- and regioselective incorporation of nucleophiles (Nu) and dienes, giving more complex, multistereocenter containing cyclopentanoids. Finally, the Ox group is readily removed and recovered or can be converted into other amine functionalities.

Studies on copper(I)-catalyzed highly regio- and stereo-selective hydroboration of alkynamides

The copper(i)-catalyzed hydroboration of alkynamides with B 2pin2 afforded the alkenamide boronates in 66% to nearly quantitative yields with high regio- and stereo-selectivity. It was interesting to note that the regio-selectivity of the reaction is opposite to that observed in the carbometallation reaction of alkynamides, and the resulting alkenyl boronates provided access to α,-disubstituted (Z)-alkenamides through further elaboration. This journal is the Partner Organisations 2014.

Copper(I)-catalyzed highly regio- and stereoselective boron addition-protonolysis of alkynamides to give alkenamides

Copper-catalyzed and highly chemoselective reduction of N-alkynylamides by a boron addition-protonolysis protocol is presented. The reaction proceeds with the addition of boryl-copper complex to N-alkynylamides with high regioselectivity and stereoselectivity, followed by regiocontrolled transmetallation of the α-site of the alkenylboronate with MeOCuL to afford N-alkenylamides in good yields. Deuterium labeling experiments indicated that both of the alkenyl hydrogen atoms originate from the additive methanol. The copper-catalyzed semireduction of N-alkynylamides by a boron addition-protonlysis protocol afforded N-alkenylamides in good yields with high stereo- and chemoselectivity. Deuterium labeling experiments indicated that both of the alkenyl hydrogen atoms of the N-alkenylamides originate from the additive methanol. Copyright

Heterogeneously catalyzed selective aerobic oxidative cross-coupling of terminal alkynes and amides with simple copper(ii) hydroxide

Simple copper(ii) hydroxide Cu(OH)2 could act as an efficient heterogeneous catalyst for selective oxidative cross-coupling of a broad range of terminal alkynes and amides using air as a sole oxidant, giving the corresponding ynamides in moderate to high yields (56-93% yields). The Royal Society of Chemistry 2012.