18859-05-7

Upstream product

• 6068-72-0 4-cyanobenzoyl chlorIde 
• 100-61-8 N-methylaniline 
• 201230-82-2 carbon monoxide 
• 623-00-7 4-bromobenzenecarbonitrile 
• 91039-08-6 O-(4-cyanophenyl) N-methyl-N-phenyl thiocarbamate 
• 66300-17-2 4-cyanophenyl chlorothionoformate 
• 767-00-0 4-cyanophenol 
• 13120-33-7 2-(methyl(phenyl)amino)-2-oxoacetic acid 
• 121-69-7 N,N-dimethyl-aniline 
• 105-07-7 4-cyanobenzaldehyde 

Downstream Products

• 1177398-83-2 N,4'-dimethyl-N-phenylbiphenyl-4-carboxamide 
• 130862-20-3 4-(methyl-phenyl-carbamoyl)-benzimidic acid ethyl ester; hydrochloride 

Relevant academic research and scientific papers

Acyl radicals from α-keto acids using a carbonyl photocatalyst: Photoredox-catalyzed synthesis of ketones

Acyl radicals have been generated from α-keto acids using inexpensive and commercially available 2-chloro-thioxanthen-9-one as the photoredox catalyst under visible light illumination. These reactive species added to olefins or coupled with aryl halides via a bipyridylstabilized Ni(II) catalyst, enabling easy access to a diverse range of ketones. This reliable, atom-economical, and eco-friendly protocol is compatible with a wide range of functional groups.

NBu4NI-catalyzed oxidative amidation of aldehydes with tertiary amines

An efficient oxidative coupling protocol for amide formation has been developed. Various tertiary amines and aromatic aldehydes were oxidized to their corresponding tertiary amides in moderate to good yields in the presence of a simple nBu4NI-catalyst.

Radical OfC transposition: A metal-free process for conversion of phenols into benzoates and benzamides

We report a metal-free procedure for transformation of phenols into esters and amides of benzoic acids via a new radical cascade. Diaryl thiocarbonates and thiocarbamates, available in a single high-yielding step from phenols, selectively add silyl radicals at the sulfur atom of the CdS moiety. This addition step, analogous to the first step of the Barton-McCombie reaction, produces a carbon radical which undergoes 1,2 OfC transposition through an O-neophyl rearrangement. The usually unfavorable equilibrium in the reversible rearrangement step is shifted forward via a highly exothermic C-S bond scission in the O-centered radical, which furnishes the final benzoic ester or benzamide product. The metal-free preparation of benzoic acid derivatives from phenols provides a potentially useful alternative to metal-catalyzed carbonylation of aryl triflates.

DIRECT CONVERSION OF PHENOLS INTO AMIDES AND ESTERS OF BENZOIC ACID

A method is provided for the preparation of an aromatic carboxylic acid aryl ester or an N-aryl aromatic carboxamide. The method comprises contacting an O,O-diaryl thiocarbonate or an O-aryl-N-aryl thiocarbamate with a reactant that regioselectively reacts with sulfur, which contact causes an O-neophyl rearrangement, thereby forming either the aromatic carboxylic acid aryl ester or the N-aryl aromatic carboxamide, respectively.

Metal-free transformation of phenols into substituted benzamides: A highly selective radical 1,2-O→C transposition in O-aryl-N-phenylthiocarbamates

Radical merry-go-round: A highly efficient metal-free transformation of phenols into benzamides is designed through one-step conversion of phenols to aryl thiocarbamates and a subsequent radical addition/rearrangement/ fragmentation cascade. Computational analysis fully rationalizes the experimentally observed selectivity. Despite the possible competition from N-C fragmentation and N-neophyl rearrangement, the transformation exclusively follows the most kinetically and thermodynamically favored O-neophyl rearrangement path.

Palladium-catalyzed carbonylation reactions of aryl bromides at atmospheric pressure: A general system based on xantphos

(Chemical Equation Presented) A method for the Pd-catalyzed carbonylation of aryl bromides has been developed using Xantphos as the ligand. This method is effective for the direct synthesis of Weinreb amides, 1° and 2° benzamides, and methyl esters from the corresponding aryl bromides at atmospheric pressure. In addition, a putative catalytic intermediate, (Xanphos)Pd(Br)benzoyl, was prepared and an X-ray crystal structure was obtained revealing an unusual cis-coordination mode of Xantphos in this palladium-acyl complex.