41656-75-1

Upstream product

• 125192-28-1 1-(4-isocyanophenyl)ethan-1-one 
• 144-62-7 oxalic acid 
• 16712-16-6 ammonium formate 
• 20062-24-2 4-azidoacetophenone 
• 1558-67-4 formic anhydride 
• 99-92-3 p-aminobenzophenone 
• 124-38-9 carbon dioxide 
• 64-18-6 formic acid 
• 100-19-6 (4-nitrophenyl)ethanone 
• 2258-42-6 formyl acetic anhydride 
• 667-27-6 Ethyl bromodifluoroacetate 
• 41784-08-1 4-acetylbenzenaminium hydrochloride 
• 77287-34-4 formamide 
• 68-12-2 N,N-dimethyl-formamide 

Downstream Products

• 2131-57-9 1-(4-isothiocyanatophenyl)ethanone 
• 125192-28-1 1-(4-isocyanophenyl)ethan-1-one 
• 145797-11-1 4-[N-[2-(2-naphthalenyloxy)ethyl]formamido]-alpha-oxobenzeneacetic acid methyl ester 

Relevant academic research and scientific papers

Metal-Free, Rapid, and Highly Chemoselective Reduction of Aromatic Nitro Compounds at Room Temperature

In this study, we developed a metal-free and highly chemoselective method for the reduction of aromatic nitro compounds. This reduction was performed using tetrahydroxydiboron [B2(OH)4] as the reductant and 4,4′-bipyridine as the organocatalyst and could be completed within 5 min at room temperature. Under optimal conditions, nitroarenes with sensitive functional groups, such as vinyl, ethynyl, carbonyl, and halogen, were converted into the corresponding anilines with excellent selectivity while avoiding the undesirable reduction of the sensitive functional groups.

An Environmentally Benign, Catalyst-Free N?C Bond Cleavage/Formation of Primary, Secondary, and Tertiary Unactivated Amides

Herein, we report an operationally simple, cheap, and catalyst-free method for the transamidation of a diverse range of unactivated amides furnishing the desired products in excellent yields. This protocol is environmentally friendly and operates under extremely mild conditions without using any promoter or additives. Significantly, this strategy has been implied in the chemoselective synthesis of a pharmaceutical molecule, paracetamol, on a gram-scale with excellent yield. We anticipate that this universally applicable strategy will be of great interest in drug discovery, biochemistry, and organic synthesis.

Hydration of Alkynes to Ketones with an Efficient and Practical Polyoxomolybdate-based Cobalt Catalyst

Hydration of alkynes to ketones is one of the most atom economical and universal methods for the synthesis of carbonyl compounds. However, the basic reaction usually requires organic ligand catalysts or harsh reaction conditions to insert oxygen into the C≡C bond. Here, we report an inorganic ligand supported cobalt (III) catalyst, (NH4)3[CoMo6O18(OH)6], which is supported by a central cobalt (III) mononucleus and a ring-shaped pure inorganic ligand composed of six MoVIO6 octahedrons to avoid the disadvantages of expensive and unrecyclable organic ligand catalysts or noble metal catalysts. Under mild conditions, the cobalt (III) catalyst can be used for the hydration of alkynes to ketones. The catalyst is non-toxic, green, and environment friendly. The catalyst can be recycled at least six times with high activity. According to control experiments, a reasonable mechanism is provided.

HCl-mediated transamidation of unactivated formamides using aromatic amines in aqueous media

We report transamidation protocol to synthesize a range of secondary and tertiary amides from weakly nucleophilic aromatic and hetero-aryl amines with low reactive formamide derivatives, utilizing hydrochloric acid as catalyst. This current acid mediated strategy is beneficial because it eliminates the need for a metal catalyst, promoter or additives in the reaction, simplifies isolation and purification. Notably, this approach conventionally used to synthesize molecules on gram scales with excellent yields and a high tolerance for functional groups.

Effective and selective direct aminoformylation of nitroarenes utilizing palladium nanoparticles assisted by fibrous-structured silica nanospheres

Abstract: Palladium nanoparticles (~ 1–3?nm, 0.4?wtpercent Pd) were uniformly distributed over the surface of fibrous silica nanospheres (KCC-1) modified via aminopropyltriethoxysilane using a fast and cost-effective palladium (II) chloride reduction process. The Pd nanoparticles (Pd NPs) distribution over the ensuing catalyst Pd/KCC-1-NH2 showed much more uniform distribution, and smaller size compared with the tedious hydrothermal reduction method. The morphological, chemical, and size analyses of Pd/KCC-1-NH2 by BET, UV–Vis spectra, XRD, HR-TEM, EDS and XPS analysis revealed that the succeeding material consist of a distinct fibrous silica nanospheres support adorn with Pd NPs. The resultant nanocatalyst was tested for the one-step reductive aminoformylation of aromatic nitro compounds using formic acid. A wide range of substituted nitroarenes including electron withdrawing, releasing, sterically hindered and multifunctional groups have been converted to corresponding aryl formamide in quantitative yields (yields up to 98percent) at moderate temperature (70?°C). Optimization study has proved that the 6 equivalent of formic acid is required and toluene was found to be the better solvent. The established practice is beneficial due to the use of formic acid as H2 source and formylating agent, easiness in handling of the catalyst and simple workup procedure with efficient catalyst reusability. Graphic abstract: [Figure not available: see fulltext.].

Mild C?F Activation in Perfluorinated Arenes through Photosensitized Insertion of Isonitriles at 350 nm

Fluorinated compounds have become important in the fields of agrochemical industry, pharmaceutical chemistry and materials sciences. Accordingly, various methods for their preparation have been developed in the past. Fluorinated compounds can be accessed via conjugation with fluorinated building blocks, via C?H fluorination or via selective activation of perfluorinated compounds to give the partially fluorinated congeners. Especially the direct activation of C?F bonds, one of the strongest σ-bonds, still remains challenging and new strategies for C?F activation are desirable. Herein a method for the photochemical activation of aromatic C?F bonds is presented. It is shown that isonitriles selectively insert into aromatic C?F bonds while aliphatic C?F bonds remain unaffected. Mechanistic studies reveal the reaction to proceed via the indirect excitation of the isonitrile to its triplet state by photoexcited acetophenone at 350 nm. Due to the relatively mild light used, the process shows high functional group tolerance and various compounds of the class of benzimidoyl fluorides are accessible from aryl isonitriles and commercially available perfluorinated arenes. (Figure presented.).

KOtBu-Promoted Transition-Metal-Free Transamidation of Primary and Tertiary Amides with Amines

This work discloses transamidation of primary and tertiary amides with a range of aryl, heteroaryl, and aliphatic amines using potassium tert-butoxide. The reaction proceeds at room temperature under transition-metal-free conditions providing secondary amides in high yields. Moreover, reaction of cyclopropyl amine with tertiary amides proceeds with ring-opening to provide a rapid access to enamides.

An efficient method for the N-formylation of amines under catalyst- and additive-free conditions

A simple catalyst- and additive-free method for the N-formylation of amines has been developed. The advantages of this protocol include a wide range of functional group tolerance, high efficiency and a lack of required extra promoters under mild conditions. This convenient strategy will provide a facile synthesis towards N-formamide natural products and pharmaceutical derivatives. A mechanism that involves difluorocarbene is proposed for this reaction.

Cobalt nanoparticles anchoring on nitrogen doped carbon with excellent performances for transfer hydrogenation of nitrocompounds to primary amines and N-substituted formamides with formic acid

Cobalt nanoparticles anchoring on nitrogen doped carbon derived from pyrolysis of a cobalt complex and chitosan were developed for reduction of nitrocompounds with neat formic acid to their corresponding amines or N-substituted formamides by switch of solvents. Characterization results revealed that most of the nitrogen atoms are present as graphitic N and pyridinic N as anchoring sites, and the cobalt nanoparticles are wrapped by nitrogen doped carbon layers, endowing the catalyst with excellent activity and superior reusability.

Palladium-Catalyzed Diarylation of Isocyanides with Tetraarylleads for the Selective Synthesis of Imines and α-Diimines

Using tetraaryllead compounds (PbAr4) as arylating reagents, isocyanides undergo selective diarylation in the presence of palladium catalysts such as Pd(OAc)2 or Pd(PPh3)4 to afford imines and/or α-diimines based on the isocyanide employed. With aliphatic isocyanides, imines are obtained preferentially, whereas α-diimines are formed in the case of electron-rich aromatic isocyanides. The differences in imine/α-diimine selectivity can be attributed to the stability of imidoylpalladium intermediates formed in this catalytic reaction. Compared with other arylating reagents, tetraaryllead compounds are excellent candidates for use in the selective transformations to imines and/or α-diimines, especially in terms of inhibiting the oligomerization of isocyanides, which results in a lower product selectivity in many transition-metal-catalyzed reactions of isocyanides.