2280-99-1

Upstream product

• 30364-57-9 4-methoxybenzoic acid 2,5-dioxo-1-pyrrolidinyl ester 
• 109-73-9 N-butylamine 
• 15866-24-7 bis-(3,5-dinitro-benzoyl)-peroxide 
• 19920-04-8 tetrakis-(4-methoxy-phenyl)-ethanone 
• 20950-96-3 (4-methoxyphenyl)carbamic acid phenyl ester 
• 79239-16-0 4-methoxybenzoic 3,5-dinitrobenzoic anhydride 
• 201230-82-2 carbon monoxide 
• 696-62-8 para-iodoanisole 
• 123-11-5 4-methoxy-benzaldehyde 
• 105-13-5 4-Methoxybenzyl alcohol 
• 100-09-4 4-methoxybenzoic acid 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 13939-06-5 molybdenum hexacarbonyl 
• 104-93-8 p-methylanizole 

Downstream Products

• 3910-58-5 N-(4-methoxybenzyl)butan-1-amine 
• 105-13-5 4-Methoxybenzyl alcohol 

Relevant academic research and scientific papers

Method for synthesizing amide by using methyl arene and amine in water phase

The invention provides a high-efficient method of synthesizing amide with methyl aromatics and amine. In the method, with the methyl aromatics and the amine as the raw materials in the water phase and TBHP and TBAI respectively as an oxidizing agent and a catalyst, a sp3 C-H bond and a sp3 N-H bond are broken and a C-N bond is formed. Compared with a conventional method of synthesizing the amide from oxidized amide, in which an activated acyl group or amine is required, the method is carried out with water as the solvent so that the method is not only economical but also environmental-protective. The method has a very good application prospect in the field of synthesizing polypeptide, protein and drugs in future.

A CO2-Catalyzed Transamidation Reaction

Transamidation reactions are often mediated by reactive substrates in the presence of overstoichiometric activating reagents and/or transition metal catalysts. Here we report the use of CO2as a traceless catalyst: in the presence of catalytic amounts of CO2, transamidation reactions were accelerated with primary, secondary, and tertiary amide donors. Various amine nucleophiles including amino acid derivatives were tolerated, showcasing the utility of transamidation in peptide modification and polymer degradation (e.g., Nylon-6,6). In particular,N,O-dimethylhydroxyl amides (Weinreb amides) displayed a distinct reactivity in the CO2-catalyzed transamidation versus a N2atmosphere. Comparative Hammett studies and kinetic analysis were conducted to elucidate the catalytic activation mechanism of molecular CO2, which was supported by DFT calculations. We attributed the positive effect of CO2in the transamidation reaction to the stabilization of tetrahedral intermediates by covalent binding to the electrophilic CO2

Rapid Organocatalytic Formation of Carbon Monoxide: Application towards Carbonylative Cross Couplings

Herein, the first organocatalytic method for the transformation of non-derivatized formic acid into carbon monoxide (CO) is introduced. Formylpyrrolidine (FPyr) and trichlorotriazine (TCT), which is a cost-efficient commodity chemical, enable this decarbonylation. Utilization of dimethylformamide (DMF) as solvent and catalyst even allows for a rapid CO generation at room temperature. Application towards four different carbonylative cross coupling protocols demonstrates the high synthetic utility and versatility of the new approach. Remarkably, this also comprehends a carbonylative Sonogashira reaction at room temperature employing intrinsically difficult electron-deficient aryl iodides. Commercial 13C-enriched formic acid facilitates the production of radiolabeled compounds as exemplified by the pharmaceutical Moclobemide. Finally, comparative experiments verified that the present method is highly superior to other protocols for the activation of carboxylic acids.

Mechanochemical Palladium-Catalyzed Carbonylative Reactions Using Mo(CO)6

Esters and amides were mechanochemically prepared by palladium-catalyzed carbonylative reactions of aryl iodides by using molybdenum hexacarbonyl as a convenient solid carbonyl source and avoiding a direct handling of gaseous carbon monoxide. Real-time monitoring of the mechanochemical reaction by in situ pressure sensing revealed that CO is rapidly transferred from Mo(CO)6 to the active catalytic system without significant release of molecular carbon monoxide.

Triethyl Phosphite/Benzoyl Peroxide Mediated Reductive Dealkylation of O-Benzoylhydroxylamines: A Cascade Synthesis of Secondary Amides

A new triethyl phosphite/benzoyl peroxide (BPO) mediated system has been developed for the synthesis of secondary amides with good to excellent yields in a single step. This unprecedented cascade process involves sequential reduction of N–O bond and benzoylation followed by dealkylation of N–C bond of O-benzoylhydroxylamines (O-BHA). The methodology is versatile as it tolerates a variety of aromatic and aliphatic O-BHA as substrates to access secondary amides.

5-Bromo-norborn-2-en-7-one derivatives as a carbon monoxide source for palladium catalyzed carbonylation reactions

Norbornenone (5b), obtained from the reaction of 2,5-dimethyl-3,4-diphenylcyclopentadienone dimer (3) with bromomaleic anhydride (4b), provides an excellent base-triggered source of carbon monoxide for palladium-catalysed carbonylation reactions. Aminocarbonylation, ketoamide synthesis, and Suzuki-Miyaura reactions of aryl iodides carried out in a two-chamber reaction vessel gave good to excellent yields of carbonylated products.

A Cyanide-Free Synthesis of Acylcyanides through Ru-Catalyzed C(sp3)-H-Oxidation of Benzylic Nitriles

A practical method for generation of acylcyanides devoid of any external cyanide sources is presented that relies on a mild Ru-catalyzed selective C?H-oxidation of benzylic nitriles. The starting materials are smoothly generated through condensation of the corresponding carboxylic acid amides using silanes. The obtained acylcyanides can be employed in a plethora of transformation as exemplified to some larger extend in the sequence of C?H-oxidation-Tischenko-rearrangement for the generation of structurally diverse benzoyloxycyanohydrines.

Tert -Butyl nitrite promoted transamidation of secondary amides under metal and catalyst free conditions

A mild and efficient method is demonstrated for the transamidation of secondary amides with various amines including primary, secondary, cyclic and acyclic amines in the presence of tert-butyl nitrite. The reaction proceeds through the N-nitrosamide intermediate and provides the transamidation products in good to excellent yields at room temperature. Moreover, the developed methodology does not require any catalyst or additives.

Towards a sustainable synthesis of amides: chemoselective palladium-catalysed aminocarbonylation of aryl iodides in deep eutectic solvents

A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been accomplished in deep eutectic solvents as environmentally benign and recyclable media, under mild conditions. The reactions proceeded with a good substrate scope, and a variety of amides have been synthesized in yields up to 98%.

Integration of co2 reduction with subsequent carbonylation: Towards extending chemical utilization of co2

Currently, it still remains a challenge to amplify the spectrum of chemical fixation of CO2, although enormous progress has been achieved in this field. In view of the widespread applications of CO in a myriad of industrial carbonylation processes, an alternative strategy is proposed in which CO2 reduction to CO is combined with carbonylation with CO generated ex situ, which affords efficiently pharmaceutically and agrochemically attractive molecules. As such, CO2 in this study was efficiently reduced by triphenysilane using CsF to CO in a sealed two-chamber reactor. Subsequently, palladium-catalyzed aminocar-bonylation, carbonylative Sonogashira coupling of aryl iodides, and rhodium(I)-mediated Pauson–Khand-type reaction proceeded smoothly to yield amides, alkynones, and bicyclic cy-clopentenones, respectively. Furthermore, the formed alkynones can further be successfully converted to a series of heterocycles, for example, pyrazoles, 3a-hydroxyisoxazolo[3,2-a]isoindol-8-(3aH)-one derivatives and pyrimidines in moderate yields. The striking features of this protocol include operational simplicity, high efficiency, and relatively broad application scope, which represents an alternative avenue for CO2 transformation.