79341-95-0

Upstream product

• 544-92-3 copper(I) cyanide 
• 95249-12-0 1-(4-aminophenyl)-2-methylpropan-1-one 
• 52129-98-3 4-propionylbenzonitrile 
• 77-78-1 dimethyl sulfate 
• 1129-35-7 4-cyanobenzoic acid methyl ester 
• 623-26-7 terephthalonitrile 
• 95-16-9 1,3-Benzothiazole 
• 1300105-83-2 α-methylthio-p-cyanoisobutyrophenone 
• 68-12-2 N,N-dimethyl-formamide 
• 2403-57-8 1-(2-methylprop-1-en-1-yl)pyrrolidine 
• 70380-44-8 4-cyano-N-isopropylbenzamide 
• 623-00-7 4-bromobenzenecarbonitrile 
• 79-30-1 isobutyryl chloride 
• 10326-99-5 2-methyl-1-(4-nitrophenyl)propan-1-one 

Downstream Products

• 1265323-78-1 4-(2-bromo-2-methylpropanoyl)benzonitrile 
• 1265323-79-2 (S)-ethyl 1-(1-(4-cyanophenyl)-2-methyl-1-oxopropan-2-yl)piperidine-3-carboxylate 
• 1265750-13-7 (3S)-ethyl 1-(1-hydroxy-1-(4-((Z)-N'-hydroxycarbamimidoyl)phenyl)-2-methylpropan-2-yl)piperidine-3-carboxylate 
• 1287302-55-9 C₁₂H₁₀N₂O 
• 1361052-20-1 C₁₇H₁₀F₅NO 

Relevant academic research and scientific papers

Enamines as Surrogates of Alkyl Carbanions for the Direct Conversion of Secondary Amides to α-Branched Ketones

A direct transformation of secondary amides into α-branched ketones with enamines as soft alkylation reagents was developed. In this reaction, enamines serve as surrogates of alkyl carbanions, rather than the conventional enolates equivalents in the Stork's reactions, which allowed for the easy introduction of alkyl groups with electrophilic functional groups. In the presence of 4 ? molecular sieves, the method can be extended to the one-pot coupling of secondary amides with aldehydes to yield ketones. (Figure presented.).

DMF as carbon source: Rh-catalyzed α-methylation of ketones

An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.

SPHINGOSINE-1-PHOSPHATE RECEPTOR AGONISTS

Disclosed are compounds of Formula (I), or a stereoisomer or a pharmaceutically acceptable salt thereof, wherein: A is formula (II) Q is a substituted 5-membered monocyclic heteroaryl group; W is CH2, O, or NH; and R1, R2, R3, R4, R5, R6, m, n, t, and x are defined herein. Also disclosed are methods of using such compounds as selective agonists for G protein-coupled receptor S1P1, and pharmaceutical compositions comprising such compounds. These compounds are useful in treating, preventing, or slowing the progression of diseases or disorders in a variety of therapeutic areas, such as autoimmune diseases and vascular disease.

Rhodium-catalyzed phenylthiolation reaction of heteroaromatic compounds using α-(phenylthio)isobutyrophenone

In the presence of catalytic amounts of RhH(PPh3)4 and 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-benzothiazoles, 1,3-benzoxazoles, and benzothiophene reacted with α-(phenylthio) isobutyrophenone giving 2-phenylthio derivatives. Reactive monocyclic heteroaromatics, 1-methyl-1,2,3,4-tetrazole and 2-cyanothiophene were also converted into the 5-phenylthio derivatives. The use of an appropriate phenylthio transfer reagent is crucial for the efficient catalyzed conversion of heteroaromatic C-H bonds into C-S bonds.

Double duty for cyanogen bromide in a cascade synthesis of cyanoepoxides

An unprecedented reaction mode of cyanogen bromide has been discovered. Under basic conditions, cyanogen bromide acts as an equivalent of both Br + and CN- to convert enolizable ketones into the corresponding cyanoepoxides in good yields. This unique reaction mode provides new, one-pot access to densely substituted cyanoepoxides from easily available ketones (see scheme). Copyright

The photochemical nucleophile-olefin combination, aromatic substitution (photo-NOCAS) reaction (Part 4): methanol-olefins, methyl 4-cyanobenzoate

Dicyanobenzene-1,4 (1) and -1,2 are known to undergo substitution upon irradiation, in the presence of an olefin, in acetonitrile-methanol (3:1) solution.The products are 1:1:1 (methanol:olefin:aromatic) adducts, substituted on the aromatic ring with loss of a cyano group.This reaction, referred to as the photo-NOCAS (nucleophile-olefin combination, aromatic substitution) reaction, has been shown to be fairly general with regard to the olefin and the nucleophile that can be incorporated.Less is known about the scope of the reaction incorporating other electron-withdrawing substituted aromatic molecules.The purpose of this study was to determine if methyl 4-cyanobenzoate (10) would also take part in this reaction, to form 4-substituted aromatic esters.Irradiation of acetonitrile-methanol solutions of 10 and olefins 2,3-dimethyl-2-butene (2) and 1-methylcyclohexene (5) gave cyclic imine esters, 11 and 13, respectively, instead of photo-NOCAS products.The photo-NOCAS products were obtained when the codonor biphenyl (4) was added to the irradiation mixture.Formation of the cyclic imine ester is attributed to excitation of the charge-transfer complex formed between 10 and the olefin.The addition of biphenyl (4) serves to generate the contact radical ion pair (CRIP) upon irradiation of the charge-transfer complex between 10 and 4.This CRIP can dissociate to the solvent-separated radical ions, the radical cation of 4 can accept an electron from the olefin, and the olefin radical cation can go on to give the photo-NOCAS products.Irradiation of a solution of 10 and 2 in nonpolar solvent (benzene) gave the oxetane, believed to arise from the exciplex.In addition to photo-NOCAS products from 10, 4-cyanophenylketones 17 and 23 are also formed by attack of the β-alkoxyalkyl radical at the carboxyl carbonyl.The differences in behaviour between 1,4-dicyanobenzene (1) and methyl 4-cyanobenzoate (10) under these reaction conditions are described and explained.

Reaction ofα- Halo Ketones with Nucleophiles

p-Nitro- or p-cyanophenacyl chloride or the 1,1-dimethyl derivatives react with the anion of 2-nitropropane to form the C-alkilation product by a radical chain mechanism (SRN1).With the 1,1-dimethyl derivatives, the free radical substitution is photostimulated and occurs in competition with ionic reactions leading to the oxiranes 5 and hydroxy ketones 6.When K+ is used as the counterion, the SRN1 process is favored by complexation with 18-crown-6. p-Nitro-1,1-dimethylphenacyl chloride gives substitution products with diethyl malonate or diethyl mthylmalonate anions via the SRN1 process, but with PhS- or p-MeC6H4SO2-, substitution occurs by competing ionic and radical processes.Propylacetylenide anion reacts to form the oxirane 13a while diethyl phosphite or thiophosphite anions yield the enol phosphate 14a or thiophosphate 14b. 1,1-Dimethylphenacyl chloride reacts by nonradical processes to give the oxirane with acetylenide anions, the substitution products with PhS- or p-MeC6H4SO2- and a mixture of the enol phosphate, and oxirane 16 with diethyl phosphite anion.With Me2C==NO2-K+, mainly the oxirane is formed in Me2SO but mainly substitution via the SRN1 chain is observed in HMPA.

The Allopolarization Principle and its Applications, IV. Substituent Effects in the Methylation of Enolate Anions

The ratio of O- and C-methylated products in the reaction of the sodium salts of acetophenones 1, propiophenones 3, phenylacetones 5, β-dicarbonyl compounds 12, α-cyanocarbonyl compounds 13, acetaldehyde, propionaldehyde, and diethylketone with dimethyl sulfate, methyl iodide, and trimethyl phosphate in HMPTA has been determined with regard to the effect of substituents.In some cases the influence of solvents, concentration and temperature has also been studied.