75920-44-4

Upstream product

• 541533-00-0 4-methyl-N'-(1-(3-methylphenyl)ethylidene)benzenesulfonohydrazide 
• 333-20-0 potassium thioacyanate 
• 585-74-0 3-Methylacetophenone 
• 100-80-1 3-methylstyrene 
• 7677-24-9 trimethylsilyl cyanide 
• 2947-60-6 3-methylbenzyl cyanide 
• 124-38-9 carbon dioxide 
• 773837-37-9 sodium cyanide 
• 88563-82-0 1-(bromoethyl)-3-methylbenzene 
• 67-56-1 methanol 
• 74-88-4 methyl iodide 

Relevant academic research and scientific papers

Asymmetric Deoxygenative Cyanation of Benzyl Alcohols Enabled by Synergistic Photoredox and Copper Catalysis?

Summary of main observation and conclusion. An enantioselective deoxygenative cyanation of benzyl alcohols was accomplished for the first time through the synergistic photoredox and copper catalysis. This reaction features the use of organic photosensitizer and low-cost 3d metal catalyst, simple and safe operations, and extremely mild conditions. A variety of chiral benzyl nitriles were produced in generally good yields and high level of enantiocontrols from readily available feedstocks (22 examples, up to 93% yield and 92% ee).

Nickel-Catalyzed Markovnikov Transfer Hydrocyanation in the Absence of Lewis Acid

Hydrocyanation in the absence of toxic HCN gas is highly desirable. Addressing that challenge, transition-metal-catalyzed transfer hydrocyanation using safe HCN precursors has been developed, but these reagents generally require a Lewis acid for activation, and the control of regioselectivity often remains problematic. In this Letter, a Ni-catalyzed highly Markovnikov-selective transfer hydrocyanation that operates in the absence of any Lewis acid is reported. The readily prepared pro-aromatic 1-isopropylcyclohexa-2,5-diene-1-carbonitrile is used as the HCN source, and the reaction shows a broad substrate scope and high functional group tolerance. Terminal styrene derivatives, dienes, and internal alkynes are converted with good to excellent selectivities. Mechanistic studies provide insights into the origin of the regioselectivity.

α-Methylation of 2-Arylacetonitrile by a Trimethylamine-Borane/CO2 System

A highly selective monomethylation of 2-arylacetonitrile using CO2 is described. The utilization of trimethylamine-borane facilitates the six-electron reduction of CO2. This reaction is the first selective six-electron reductive functionalization of CO2 faciliated by C(sp3)-H bonds. A variety of 2-arylpropionitrile was obtained in good yields. The reaction could also be applied at the gram scale.

Enantioseparation of Sulfoxides and Nitriles by Inclusion Crystallization with Chiral Organic Salts Based on l-Phenylalanine

Enantioselective inclusion of aromatic sulfoxides and nitriles was achieved in a host framework created by organic salts comprising achiral benzoic acids and a chiral primary amine (1a) derived from l-phenylalanine. Tuning of the combined achiral acid component successfully changed the chiral recognition ability of the organic salts. The guest molecules were hydrogen-bonded to form three-component inclusion crystals, and the enantiomers of nitriles and sulfoxides were separated with high selectivity up to 92 and 98 % ee. As far as we know, this is the first example of the enantioseparation of non-functionalized aromatic nitriles.

Ex situ generation of stoichiometric HCN and its application in the Pd-catalysed cyanation of aryl bromides: Evidence for a transmetallation step between two oxidative addition Pd-complexes

A protocol for the Pd-catalysed cyanation of aryl bromides using near stoichiometric and gaseous hydrogen cyanide is reported for the first time. A two-chamber reactor was adopted for the safe liberation of ex situ generated HCN in a closed environment, which proved highly efficient in the Ni-catalysed hydrocyanation as the test reaction. Subsequently, this setup was exploited for converting a range of aryl and heteroaryl bromides (28 examples) directly into the corresponding benzonitriles in high yields, without the need for cyanide salts. Cyanation was achieved employing the Pd(0) precatalyst, P(tBu)3-Pd-G3 and a weak base, potassium acetate, in a dioxane-water solvent mixture. The methodology was also suitable for the synthesis of 13C-labelled benzonitriles with ex situ generated 13C-hydrogen cyanide. Stoichiometric studies with the metal complexes were undertaken to delineate the mechanism for this catalytic transformation. Treatment of Pd(P(tBu)3)2 with H13CN in THF provided two Pd-hydride complexes, (P(tBu)3)2Pd(H)(13CN), and [(P(tBu)3)Pd(H)]2Pd(13CN)4, both of which were isolated and characterised by NMR spectroscopy and X-ray crystal structure analysis. When the same reaction was performed in a THF : water mixture in the presence of KOAc, only (P(tBu)3)2Pd(H)(13CN) was formed. Subjection of this cyano hydride metal complex with the oxidative addition complex (P(tBu)3)Pd(Ph)(Br) in a 1 : 1 ratio in THF led to a transmetallation step with the formation of (P(tBu)3)2Pd(H)(Br) and 13C-benzonitrile from a reductive elimination step. These experiments suggest the possibility of a catalytic cycle involving initially the formation of two Pd(ii)-species from the oxidative addition of LnPd(0) into HCN and an aryl bromide followed by a transmetallation step to LnPd(Ar)(CN) and LnPd(H)(Br), which both reductively eliminate, the latter in the presence of KOAc, to generate the benzonitrile and LnPd(0).

Methylation of C(sp3)-H/C(sp2)-H bonds with methanol catalyzed by cobalt system

A highly efficient Co-based catalytic system, composed of a commercially available Co salt, a tetradentate phosphine ligand P-(CH2CH2PPh2)3(PP3), and a base (denoted as [Co]/PP3/base), is developed for the methylation of C(sp3)-H and C(sp2)-H bonds using methanol as a methylating reagent. The Co(BF4)2.6H2O/PP3/K2CO3 catalytic system showed high catalytic activity for the methylation of C-H bonds in aryl alkyl ketones, aryl acetonitriles, and indoles, with wide substrate scope and good functional group tolerance, and methylsubstituted products were obtained in good to excellent yields at 100 °C. This cheap, readily available, and highly efficient Co-based catalytic system may have promising applications in methylation reaction using methanol.

Copper-Catalyzed Cyanation of N-Tosylhydrazones with Thiocyanate Salt as the "cN" Source

A novel protocol for the synthesis of α-aryl nitriles has been successfully achieved via a copper-catalyzed cyanation of N-tosylhydrazones employing thiocyanate as the source of cyanide. The features of this method include a convenient operation, readily available substrates, low-toxicity thiocyanate salts, and a broad substrate scope.