28289-83-0

Upstream product

• 41412-79-7 1-(3-chloroprop-1-ynyl)-4-nitrobenzene 
• 459-57-4 4-fluorobenzaldehyde 
• 100-52-7 benzaldehyde 
• 586-78-7 para-nitrophenyl bromide 
• 61266-32-8 3-(4-nitrophenyl)prop-2-yn-1-ol 
• 5332-96-7 1-(4-nitrophenyl)propan-2-one 
• 74-99-7 prop-1-yne 
• 100-19-6 (4-nitrophenyl)ethanone 
• 27491-70-9 dimethyl diazomethylphosphonate 
• 636-98-6 p-nitrobenzene iodide 
• 30645-13-7 copper(I) metylacetylenide 
• 860519-10-4 2-chloro-1-(4-nitro-phenyl)-propene 
• 141-52-6 sodium ethanolate 
• 58335-31-2 1,3-dilithiopropyne 

Downstream Products

• 2735-14-0 1,2-bis(4-nitrophenyl)acetylene 
• 503-17-3 dimethylacetylene 

Relevant academic research and scientific papers

Xantphos-coordinated palladium dithiolates: Highly efficient catalyst for decarboxylative Sonogashira reaction into corresponding alkynes

This work reports Xantphos-coordinated palladium dithiolate complexes as catalysts for decarboxylative Sonogashira coupling reaction of phenyl propiolic acid and 2-butynoic acid with various iodoarenes. These palladium aryl dithiolate complexes were synthesized and characterized by 1H and 31P nuclear magnetic resonance (NMR) spectroscopy, melting point, and elemental analysis (CHNS). Synthetic utility for the reported protocol is explored for the effect of various functional groups on the yield of corresponding heteroaryl alkynes. The current protocol showed excellent catalytic activity towards decarboxylative alkynylation reaction with high turn-over number (TON) up to 105 and turn-over frequency (TOF) up to 104 h?1. The catalyst could be recycled up to six recycles without losing its catalytic activity. The in situ generation of palladium nanoparticles (PdNPs) was observed after the third recycle, and the amount was significant after the sixth recycle, which were confirmed and characterized by powder X-ray diffraction (XRD), scanning electron microscope (SEM), and energy-dispersive X-ray (EDX) analysis and high-resolution transmission electron microscopy (HR-TEM). The catalytic activity of the reaction is attributed to the formation of PdNPs.

Regiospecific palladium-catalyzed cross-coupling reactions using the operational equivalent of 1,3-dilithiopropyne

A regiospecific palladium-catalyzed cross-coupling reaction using the operational equivalent of the dianion 1,3-dilithiopropyne, with aromatic iodides is reported. This reaction gives high yields of 1-propyn-1-yl-benzenes and 2-(propyn-1-yl)thiophenes in

Transformation of Carbonyl Compounds into Homologous Alkynes under Neutral Conditions: Fragmentation of Tetrazoles Derived from Cyanophosphates

Cyanophosphates (CPs) can be easily prepared from either ketones or aldehydes, and their reaction with NaN3-Et3N·HCl results in the formation of azidotetrazoles. Under microwave irradiation, successive fragmentation of the azidotetrazoles generates alkylidene carbenes that undergo [1,2]-rearrangement and are transformed into homologous alkynes. Treatment of ketone-derived CPs with TMSN3 and Bu2SnO as catalyst in toluene at reflux directly yields the corresponding internal alkynes, whereas the reaction of aldehyde-derived CPs with NaN3-Et3N·HCl in THF at reflux or TMSN3-Bu2SnO (cat.) in toluene at reflux provides homologous terminal alkynes in good yields. These reactions take place under neutral conditions and can be successfully extended to obtain alkynes that are not usually accessible from the corresponding carbonyl compounds by the Ohira-Bestmann or Shioiri procedures, which require basic conditions.

Palladium-catalyzed allylation of tautomerizable heterocycles with alkynes

A method for the allylic amidation of tautomerizable heterocycles was developed by a palladium catalyzed allylation reaction with 100% atom economy. A series of structurally diverse N-allylic substituted heterocycles can be synthesized in good yields with high chemo-, regio-, and stereoselectivities under mild conditions.

Stereoselective Photoredox-Catalyzed Chlorotrifluoromethylation of Alkynes: Synthesis of Tetrasubstituted Alkenes

A new photoredox-catalyzed chlorotrifluoromethylation reaction of internal arylalkynes under mild conditions using visible light has been developed. The reactions proceed with high levels of regio- and stereoselectivity and utilize commercially available CF3SO2Cl as both the CF3 and Cl source. In the mechanistic pathway for this process, generation of the CF3 radical and chloride ion occurs by Ir(ppy)3-photocatalyzed reductive decomposition of CF3SO2Cl. The synthetically important trifluoromethyl-substituted vinyl chlorides produced in this process can be readily transformed to 1,1-bis-arylalkenes by using Suzuki coupling.

Palladium and copper catalyzed Sonogashira decarboxylative coupling of aryl iodides and alkynyl carboxylic acids

A mild procedure of palladium and copper catalyzed decarboxylative cross-coupling reaction of aryl halides and alkynyl carboxylic acids has been developed. Low molecular weight acids, to introduce small building blocks, were specifically used. This method

Palladacycle-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl chlorides under air

A highly efficient and practical protocol for palladacycle-catalyzed decarboxylative coupling of alkynyl carboxylic acids with aryl chlorides was developed. The reaction could proceed smoothly in air within 3 h under optimized reaction conditions (1 mol % of palladacycle, 4 mol % of Xphos, 2.0 equiv of K2CO3 in xylene/H2O), affording the corresponding internal alkynes in mostly good to excellent yields. Remarkably, this result represents the first successful examples of this type of decarboxylative cross-coupling using electron-poor, electron-neutral and even inactive sterically hindered electron-rich aryl chlorides as the starting materials.

Original TDAE strategy using propargylic chloride: Rapid access to 1,4-diarylbut-3-ynol derivatives

We report herein the first synthesis of propargylic alcohols using an organic reducing agent. Diarylbutynol derivatives are formed in moderate to good yields under mild conditions from the reaction of 1-(3-chloroprop-1-ynyl)-4- nitrobenzene with various aromatic aldehydes using tetrakis(dimethylamino) ethylene (TDAE) as reductant.

Alkyne metathesis with simple catalyst systems: High yield dimerization of propynylated aromatics; scope and limitations

High yield dimerization of propynylated benzenes and propynylnaphthalene by a mixture of Mo(CO)6 and 4-chlorophenol at 140 °C in 1,2-dichlorobenzene is reported to give the corresponding disubstituted alkynes. The scope and limitation of the reaction and the influence of substitution pattern and substitution type are discussed. Oxygen or nitrogen carrying substrates metathesize in moderate to good yields and ortho-alkyl substituted examples form the respective tolanes very efficiently.

Diazoethenes: Their Attempted Synthesis from Aldehydes and Aromatic Ketones by Way of the Horner-Emmons Modification of the Wittig Reaction. A Facile Synthesis of Alkynes

The base-promoted reaction of dimethyl (diazomethyl)phosphonate (8) with aldehydes and aryl ketones at low temperatures has been investigated.Alkynes, in modest to excellent yields, are the predominant products of these reactions, a result consistent with the intervention of diazoethenes (3).The latter appear to be unstable toward unimolecular decomposition at -78 deg C and yield nitrogen and alkylidenecarbenes (1).