1297609-84-7

Upstream product

• 875-51-4 4-Bromo-2-nitroaniline 
• 292638-85-8 acrylic acid methyl ester 
• 67-56-1 methanol 
• 140-88-5 ethyl acrylate 

Relevant academic research and scientific papers

Synthesis of Indoles by Reductive Cyclization of Nitro Compounds Using Formate Esters as CO Surrogates

Alkyl and aryl formate esters were evaluated as CO sources in the Pd- and Pd/Ru-catalyzed reductive cyclization of 2-nitrostyrenes to give indoles. Whereas the use of alkyl formates requires the presence of a ruthenium catalyst such as Ru3(CO)12, the reaction with phenyl formate can be performed by using a Pd/phenanthroline complex alone. Phenyl formate was found to be the most effective CO source and the desired products were obtained in excellent yields, often higher than those previously reported using pressurized CO. The reaction tolerates many functional groups, including sensitive ones like a free aldehydic group or a pendant pyrrole. Detailed experiments and kinetic studies allow to conclude that the activation of phenyl formate is base-catalyzed and that the metal doesn't play a role in the decarbonylation step. The reactions can be performed in a single thick-walled glass tube with as little as 0.2 mol-% palladium catalyst and even on a 2 g scale. The same protocol can be extended to other nitro compounds, affording different heterocycles.

Multibond Forming Tandem Reactions of Anilines via Stable Aryl Diazonium Salts: One-Pot Synthesis of 3,4-Dihydroquinolin-2-ones

A fast and effective one-pot tandem process that generates Heck coupled products from readily available anilines via stable aryl diazonium tosylate salts was developed. The mild and simple procedure involves rapid formation of aryl diazonium salts using a polymer-supported nitrite reagent and p-tosic acid, followed by a base-free Heck-Matsuda coupling with acrylates and styrenes. Using 2-nitroanilines as substrates, the one-pot tandem process was extended for the direct synthesis of 3,4-dihydroquinolin-2-ones. In this case, following diazotization and Heck-Matsuda coupling to give methyl cinnamates, addition of hydrogen and reutilization of the palladium catalyst for reduction of the nitro group and hydrogenation of the alkene resulted in efficient formation of 3,4-dihydroquinolin-2-ones. The synthetic utility of this one-pot, four-stage process was demonstrated with the five-pot synthesis of a quinolinone-based sodium ion channel modulator.

Palladium Nanoparticles Supported on Sulfonic Acid Functionalized Silica as Trifunctional Heterogeneous Catalysts for Heck and Suzuki Reactions

The arylation of acrylates and boronic acids with anilines, through in situ generated aryl diazonium salts, was successfully achieved by using trifunctional heterogeneous catalysts bearing Br?nsted acid and metal active sites. The trifunctional materials were prepared by adsorption of palladium nanoparticles, generated by reduction of a solution of Pd(OAc)2 onto a commercially available sulfonic acid functionalized silica. These new trifunctional catalysts act as a 1) proton donor for the diazotization step, 2) counterion for the diazonium salt, and 3) Pd source for the coupling step. This unprecedented strategy, features mild and safe conditions as hazardous aryl diazonium salts are generated in situ and only produces environmentally friendly byproducts such as tBuOH, H2O, and N2.

Heck-Matsuda arylation of olefins through a bicatalytic approach: Improved procedures and rationalization

The scope of the palladium-catalyzed Heck-Matsuda reaction, proceeding through the catalytic activation of anilines into the corresponding diazonium salts, has been considerably extended and is now working with deactivated electrophiles. Two different procedures, using catalytic amounts of both palladium and acid, have been optimized allowing the concept of bicatalysis to cover the complete electronic range of anilines. These environmentally friendly procedures proceed under very mild conditions, at room temperature in methanol, and only generate tert-butyl alcohol, water and nitrogen as by-products. Rationalization of reaction outcomes encountered in this work has been discussed with the support of computational studies.

Unprecedented substoichiometric use of hazardous aryl diazonium salts in the Heck-Matsuda reaction via a double catalytic cycle

The first Heck-Matsuda reaction using a catalytic amount of diazonium salts has been discovered. The reaction proceeds through an unprecedented double catalytic cycle in which the electrophile is in situ generated through the reaction advancement. This concept features mild and safe conditions as hazardous aryl diazonium salts are not isolated anymore. Importantly, this sustainable procedure generates only environmentally friendly byproduct such as t-BuOH, H2O, and N2.