62501-58-0

Upstream product

• 5068-02-0 <(4-Nitro-benzoyl)-cyan-methylen>-triphenylphosphoran 
• 555-16-8 4-nitrobenzaldehdye 
• 545-06-2 trichloroacetonitrile 
• 122-04-3 4-nitro-benzoyl chloride 
• 937-31-5 (4-Nitrophenyl)acetylene 
• 105-56-6 ethyl 2-cyanoacetate 
• 613-90-1 benzoyl cyanide 
• 2888-10-0 β-Chlor-p-nitro-zimtaldehyd 
• 636-98-6 p-nitrobenzene iodide 
• 61266-32-8 3-(4-nitrophenyl)prop-2-yn-1-ol 

Downstream Products

• 127956-34-7 1,2-dihydro-2-(4-nitrobenzoyl-cyanomethylidene)-1-methyl-pyridine 

Relevant academic research and scientific papers

An aerobic and green C-H cyanation of terminal alkynes

This study describes a benign C-H cyanation of terminal alkynes with α-cyanoesters serving as a nontoxic cyanide source. In situ generation of the key copper cyanide intermediate is proposed by a sequence of α-C-H oxidation and copper-mediated β-carbon elimination of α-cyanoesters, releasing the α-ketoester byproduct observed experimentally. The ensuing reaction of copper cyanide with terminal alkynes delivers preferentially cyanoalkynes and surpasses the possible Glaser type dimerization of terminal alkynes or the undesired accumulation of HCN under protic conditions. The presence of the co-oxidant K2S2O8 is crucial to this selectivity, probably by promoting oxidative transmetalation and the resulting formation of the Cu(iii)(acetylide)(CN) intermediate. All the reagents and salts used are commercially available, cheap and nontoxic, avoiding the use of highly toxic cyanide salts typically required in cyanation studies. The scope of this reaction is demonstrated with a set of alkynes and α-cyanoesters. The application of this method to late-stage functionalization of the terminal alkyne group in an estrone derivative is also feasible, showing its practical value for drug design.

Chemo- And regioselective click reactions through nickel-catalyzed azide-alkyne cycloaddition

Metal-catalyzed cycloaddition is an expeditious synthetic route to functionalized heterocyclic frameworks. However, achieving reactivity-controlled metal-catalyzed azide-alkyne cycloadditions from competing internal alkynes has been challenging. Herein, we report a nickel-catalyzed [3 + 2] cycloaddition of unsymmetrical alkynes with organic azides to afford functionalized 1,2,3-triazoles with excellent regio- and chemoselectivity control. Terminal alkynes and cyanoalkynes afford 1,5-disubstituted triazoles and 1,4,5-trisubstituted triazoles bearing a 4-cyano substituent, respectively. Thioalkynes and ynamides exhibit inverse regioselectivity compared with terminal alkynes and cyanoalkynes, affording 1,4,5-trisubstituted triazoles with 5-thiol and 5-amide substituents, respectively. Density functional theory calculations are performed for the elucidation of the reaction mechanism. The computed mechanism suggests that a nickellacyclopropene intermediate is generated by the oxidative addition of the alkyne substrate to the Ni(0)-Xantphos catalyst, and the subsequent C-N coupling of this intermediate with an azide is responsible for the chemo- and regioselectivity.

Palladium-Catalyzed Nitrile-Assisted C(sp3)-Cl Bond Formation for Synthesis of Dichlorides

A palladium-catalyzed coupling procedure of alkenes with alkynylnitriles has been demonstrated for the synthesis of dichlorides. The reaction is the first example of nitrile-assisted C(sp3)-Cl formation promoted by coordination of a cyano group with an alkylpalladium(II) complex. The construction of a five-membered cycle intermediate successfully inhibits the β-hydride abstraction, resulting in direct C-Cl bond reductive elimination of alkylpalladium(II) chloride.

Copper-catalyzed direct cyanation of terminal alkynes with benzoyl cyanide

Copper-catalyzed direct cyanation of terminal alkynes is achieved using less toxic, stable and easy to handle benzoyl cyanide as a cyanide source and air as an oxidant. This protocol provides a good alternative to the preparation of 3-arylpropiolonitriles

Transition Metal-Free Approach to Propynenitriles and 3-Chloropropenenitriles

A transition metal-free, facile and efficient one-pot protocol for the synthesis of propynenitriles from readily available 3-chloropropenals is disclosed. The reaction conditions have also been optimized for the exclusive formation and isolation of 3-chloropropenenitriles which are important building blocks in general and are intermediates in the synthesis of propynenitriles. The hallmark of the methodology is the use of non-toxic reagents, milder, metal-free and economically benign reaction conditions avoiding a harsh dehydration step while achieving excellent yields.

One-pot synthesis of conjugated alkynenitriles from aldehydes

A method of preparing conjugated alkynenitriles was developed from various aldehydes with CCl3CN and PPh3 in the presence of tBuLi. The reaction proceeded via α-chlorovinyl nitrile as an intermediate without any side react

Microwave assisted intramolecular wittig reaction: A facile method for the synthesis of conjugated acetylenes

A rapid and efficient synthesis of acetylenic compounds by the microwave assisted intramolecular Wittig reaction of β-oxo-alkylidene-triphenylphosphoranes is reported.

Synthesis of Conjugated Alkynenitriles

The synthesis of 2-butynenitrile (7a), 3-(4-methoxyphenyl)-(7b)-, 3-(4-ethoxyphenyl)-(7c)-, 3-(4-nitrophenyl)-(7d)- and 3-(3,4,5-trimethoxyphenyl)-(7e)-propynenitriles by thermal decomposition of the corresponding acylcyanomethylenetriphenylphosphoranes (6a-e) is described.The ethoxycarbonylcyanomethylenetriphenylphosphorane (6f) under the same conditions does not give the alkynenitrile.Cleavage to triphenylphosphine oxide and acetylenic nitrile is the predominant fragmentation observed in the mass spectra of all the ylids.