20432-30-8

Upstream product

• 91-48-5 (E)-2,3-diphenylpropenoic acid 
• 103-84-4 Acetanilid 
• 100-52-7 benzaldehyde 
• 77382-18-4 dibenzyl diphenyl phosphonium bromide 
• 91-47-4 (Z)-2,3-diphenylprop-2-enoic acid 
• 103-80-0 phenylacetyl chloride 
• 62-53-3 aniline 
• 621-06-7 2,N-diphenylacetamide 
• 100-51-6 benzyl alcohol 
• 13440-24-9 anti-1,2-dibromo-1,2-diphenylethane 
• 14447-41-7 (E)-1-bromo-1,2-diphenylethene 
• 103-71-9 phenyl isocyanate 
• 886-38-4 diphenylcyclopropenone 
• 108-95-2 phenol 

Downstream Products

• 38035-81-3 3-phenyl-1H-quinolin-2-one 

Relevant academic research and scientific papers

Manganese(I) Catalyzed α-Alkenylation of Amides Using Alcohols with Liberation of Hydrogen and Water

Herein, unprecedented manganese-catalyzed direct α-alkenylation of amides using alcohols is reported. Aryl amides are reacted with diverse primary alcohols, which provided the α,β-unsaturated amides in moderate to good yields with excellent selectivity. Mechanistic studies indicate that Mn(I) catalyst oxidizes the alcohols to their corresponding aldehydes and also plays an important role in efficient C═C bond formation through aldol condensation. This selective olefination is facilitated by metal-ligand cooperation by the aromatization-dearomatization process operating in the catalytic system. Biorenewable alcohols are used as alkenylation reagents for the challenging α-alkenylation of amides with the highly abundant base metal manganese as a catalyst, which results in water and dihydrogen as the only byproduct, making this catalytic transformation attractive, sustainable, and environmentally benign.

Regioselective Synthesis of α-Functional Stilbenes via Precise Control of Rapid cis- trans Isomerization in Flow

The rapid cis-trans isomerization of α-anionic stilbene was regioselectively controlled by using flow microreactors, and its reaction with various electrophiles was conducted. The reaction time was precisely controlled within milliseconds to seconds at -50 °C to selectively give the cis- or trans-isomer in high yields. This synthetic method in flow was well-applied to synthesize precursors of commercial drug compound, (E)- and (Z)-tamoxifen with high regioselectivity and productivity.

Palladium-Catalyzed C-C Bond Activation of Cyclopropenone: Modular Access to Trisubstituted α,β-Unsaturated Esters and Amides

Strain-driven palladium/N-heterocyclic carbene-catalyzed C-C bond activation of diphenylcyclopropenone (DPC) has been explored for one-step access to trisubstituted α,β-unsaturated esters and amides. The designed transformation works under mild conditions providing exclusively a single stereoisomer. Mechanistic studies support the oxidative addition of the C-C bond of cyclopropenone to in-situ-generated Pd(0) intermediate. We have proved that vinylic hydrogen in the product is coming from phenol/aniline through deuterium-labeling studies. Late-stage functionalization of bioactive molecules such as procaine, estrone, and hymecromone demonstrates the robustness of this protocol.

A Palladium-Catalyzed Cascade C-C Activation of Cyclopropenone and Carbonylative Amination: Easy Access to Highly Functionalized Maleimide Derivatives

We describe herein the first report on palladium-catalyzed C-C bond activation of cyclopropenone and concomitant carbonylative amination to produce maleimides. The interesting aspect of this reaction is that the sacrificial elimination of carbon monoxide from the substrate is efficiently recaptured by one of the intermediates in the catalytic cycle for the formation of maleimides. 18O isotopic studies confirmed that the source of carbon monoxide is from cyclopropenone.

Stereospecific Electrophilic Fluorocyclization of α,β-Unsaturated Amides with Selectfluor

An efficient fluorocyclization of α,β-unsaturated amides through a formal halocyclization process is developed. The reaction proceeds under transition-metal-free conditions and leads to the formation of fluorinated oxazolidine-2,4-diones with excellent regio- and diastereoselectivity. The evaluation of the reaction mechanism based on preliminary experiments and density functional theory calculations suggests that a synergetic syn-oxo-fluorination occurs and is followed by an anti-oxo substitution reaction. The reaction opens a new window in the field of stereospecific fluorofunctionalization.

Stereoselective formal hydroamidation of si-substituted arylacetylenes with DIBAL-H and isocyanates: Synthesis of (E)- And (Z)-α-Silyl-α,β-unsaturated amides

An efficient and stereoselective method for the synthesis of (E)- and (Z)-α-silyl-α,β-unsaturated amides and its synthetic applications are presented herein. The solvent-controlled hydroaluminations of Si-substituted alkynes with DIBAL-H generate diastereomerically enriched alkenylaluminum reagents that are directly reacted with isocyanates at ambient temperature to afford α-silyl-α,β-unsaturated amides in high yields with retained stereoselectivity. In particular, this process enables the synthesis of a broad range of (E)-α-silyl-α,β- unsaturated amides, which are the less studied isomers. The synthetic utility of this method is highlighted by its short reaction time, ease of purification, easily accessible substrates and reagents, gram-scale synthesis, and the further transformations of C-Si bonds into C-H, C-X, and C-C bonds.

Titanium-Promoted Cross-Coupling for the Selective Synthesis of Polysubstituted, Conjugated Amides

α,β-Unsaturated amides are important building blocks and are key structural elements in a number of biologically active natural products. Despite their importance and prevalence, few methods exist to prepare conjugated amides directly and modularly. To address this gap, a titanium-promoted coupling of alkynes and isocyanates has been developed. The method is highly stereoselective, producing only the E isomer with good chemoselectivity and regioselectivity (>95/5), for unsymmetrical internal alkynes that contain a steric bias. The reactive titanacyclopentene intermediate formed from the coupling of the alkyne and isocyanate was additionally reacted with various electrophiles to access tetrasubstituted enamides.

β-LACTAM FORMATION VIA ENOLATE ADDITION: AN UNEXPECTED METHYLENATION REACTION

The condensation of ethyl phenylacetate or ethyl β-hydroxybutyrate with Schiff bases in presence of an excess of lithium diisopropylamide or lithium hexamethyldisilazide leads to unsaturated amides instead of the expected β-lactams.

Condensation of Lithium Diphenylphosphonium Diylides with Carbonic Anhydride Derivatives. A New One-Pot Synthesis of α,β-Unsaturated Anilides and Amidines.

Lithium diphenylphosphonium diylides readily attack phenylisocyanate and dicyclohexylcarbodiimide.The formed semi-stabilised ylides bear a metallated amide or amidine functium.Their use in situ as Wittig reagents towards aldehydes and ketones is shown to be a new one-pot, E-stereoselective synthesis for α,β-unsaturated anilides and amidines.Moreover, the corresponding phosphonium salts were isolated.Key Words: lithium phosphonium diylides; pseudo-acylation reaction; Wittig-reaction; vinylic amides and amidines.

MODELLKOMPLEX DES NICKELS FUER DIE C-C VERKNUEPFUNG VON ALKINEN MIT ISOCYANATEN

Azanickelacyclopenten derivatives, which can easily be prepared from alkynes, sicoyanantes and nickel(0) compounds, are shown to be intermediates in the nickel-catalysed synthesis of 2-pyridones.