42007-05-6

Upstream product

• 4755-50-4 4-(dimethylamino)benzoyl chloride 
• 100-10-7 4-dimethylamino-benzaldehyde 
• 201230-82-2 carbon monoxide 
• 698-70-4 4-Iodo-N,N-dimethylaniline 
• 4472-41-7 d₇-N,N-dimethylformamide 
• 121-69-7 N,N-dimethyl-aniline 
• 619-84-1 p-N,N-dimethylaminobenzoic acid 

Downstream Products

• 100-10-7 4-dimethylamino-benzaldehyde 
• 1202-25-1 methyl 4-(N,N-dimethylamino)benzoate 
• 1703-46-4 N,N-dimethyl-4-hydroxymethylaniline 

Relevant academic research and scientific papers

N-Heterocyclic Carbene Catalyzed Deuteration of Aldehydes in D 2 O

An N-heterocyclic carbene (NHC)-catalyzed direct deuteration of aldehydes in a mixed solvent of deuterium oxide (D 2 O) and cyclopentyl methyl ether was established. The present deuteration is possibly initiated by the formation of a Breslow intermediate from the aldehyde and the NHC, with subsequent trapping by D 2 O providing the monodeuterated aldehyde.

SYNTHESIS OF DEUTERATED ALDEHYDES

Described are methods for preparing a deuterated aldehyde using N-heterocyclic carbene catalysts in a solvent comprising D2O. The methods may be used to convert a wide variety of aldehydes (e.g., aryl, alkyl, or alkenyl aldehydes) to C-1 deuterated aldehydes under mild reaction conditions without functionality manipulation.

Tuning the Reactivity of a Heterogeneous Catalyst using N-Heterocyclic Carbene Ligands for C?H Activation Reactions

We report the dramatic impact of the addition of N-heterocyclic carbenes (NHCs) on the reactivity and selectivity of heterogeneous Ru catalysts in the context of C?H activation reactions. Using a simple and robust method, we prepared a series of new air-stable catalysts starting from commercially available Ru on carbon (Ru/C) and differently substituted NHCs. Associated with C?H deuteration processes, depending on Ru/C-NHC ratios, the chemical outcome can be controlled to a large extent. Indeed, tuning the reactivity of the Ru catalyst with NHC enabled: 1) increased chemoselectivity and the regioselectivity for the deuteration of alcohols in organic media; 2) the synthesis of fragile pharmaceutically relevant deuterated heterocycles (azine, purine) that are otherwise completely reduced using unmodified commercial catalysts; 3) the discovery of a novel reactivity for such heterogeneous Ru catalysts, namely the selective C-1 deuteration of aldehydes.

Dehydrogenative Coupling of Aldehydes with Alcohols Catalyzed by a Nickel Hydride Complex

A nickel hydride complex, {2,6-(iPr2PO)2C6H3}NiH, has been shown to catalyze the coupling of RCHO and R′OH to yield RCO2R′ and RCH2OH, where the aldehyde also acts as a hydrogen acceptor and the alcohol also serves as the solvent. Functional groups tolerated by this catalytic system include CF3, NO2, Cl, Br, NHCOMe, and NMe2, whereas phenol-containing compounds are not viable substrates or solvents. The dehydrogenative coupling reaction can alternatively be catalyzed by an air-stable nickel chloride complex, {2,6-(iPr2PO)2C6H3}NiCl, in conjunction with NaOMe. Acids in unpurified aldehydes react with the hydride to form nickel carboxylate complexes, which are catalytically inactive. Water, if present in a significant quantity, decreases the catalytic efficiency by forming {2,6-(iPr2PO)2C6H3}NiOH, which causes catalyst degradation. On the other hand, in the presence of a drying agent, {2,6-(iPr2PO)2C6H3}NiOH generated in situ from {2,6-(iPr2PO)2C6H3}NiCl and NaOH can be converted to an alkoxide species, becoming catalytically competent. The proposed catalytic mechanism features aldehyde insertion into the nickel hydride as well as into a nickel alkoxide intermediate, both of which have been experimentally observed. Several mechanistically relevant nickel species including {2,6-(iPr2PO)2C6H3}NiOC(O)Ph, {2,6-(iPr2PO)2C6H3}NiOPh, and {2,6-(iPr2PO)2C6H3}NiOPh·HOPh have been independently synthesized, crystallographically characterized, and tested for the catalytic reaction. While phenol-containing molecules cannot be used as substrates or solvents, both {2,6-(iPr2PO)2C6H3}NiOPh and {2,6-(iPr2PO)2C6H3}NiOPh·HOPh are efficient in catalyzing the dehydrogenative coupling of PhCHO with EtOH.

Deoxygenative Deuteration of Carboxylic Acids with D2O

We report a general, practical, and scalable means of preparing deuterated aldehydes from aromatic and aliphatic carboxylic acids with D2O as an inexpensive deuterium source. The use of Ph3P as an O-atom transfer reagent can facilitate the deoxygenation of aromatic acids, while Ph2POEt is a better O-atom transfer reagent for aliphatic acids. The highly precise deoxygenation of complex carboxylic acids makes this protocol promising for late-stage deoxygenative deuteration of natural product derivatives and pharmaceutical compounds.

Method for preparing deuterated aldehyde from carboxylic acid using iridium complex as catalyst under irradiation of blue light

A method for preparing deuterated aldehyde from carboxylic acid using an iridium complex as a catalyst under the irradiation of blue light is as follows: aromatic carboxylic acid (ArCOOH) used as a raw material and triphenylphosphine used as a deoxidizing agent are irradiated by blue light in a solution of dichloromethane and heavy water, in the atmosphere of argon, under the condition of dipotassium phosphate used as alkali and using [Ir(dF(CF3)ppy)2(dtbbpy)]PF6 as a photocatalyst and thiophenol 2,4,6-triisopropylbenzenethiol as an organic small molecule catalyst to obtain a deuterated aromatic aldehyde compound; or aliphatic carboxylic acid (Alk-COOD) used as the raw material and diphenylethoxyphosphine used as a deoxidizing agent are irradiated by blue light in a solution of toluene, inthe atmosphere of argon and under the condition of 2,6-lutidine used as alkali to obtain a deuterated fatty aldehyde compound.

Palladium/Rhodium Cooperative Catalysis for the Production of Aryl Aldehydes and Their Deuterated Analogues Using the Water–Gas Shift Reaction

A novel Pd/Rh dual-metallic cooperative catalytic process has been developed to effect the reductive carbonylation of aryl halides in moderate to good yield. In this reaction, water is the hydride source, and CO serves both as the carbonyl source and the terminal reductant through the water–gas shift reaction. The catalytic generation of the Rh hydride allows for the selective formation of highly hindered aryl aldehydes that are inaccessible through previously reported reductive carbonylation protocols. Moreover, aldehydes with deuterated formyl groups can be efficiently and selectively synthesized using D2O as a cost-effective deuterium source without the need for presynthesizing the aldehyde.

Mechanistic study on the solution-phase n-doping of 1,3-dimethyl-2-aryl-2, 3-dihydro-1H-benzoimidazole derivatives

The discovery of air-stable n-dopants for organic semiconductor materials has been hindered by the necessity of high-energy HOMOs and the air sensitivity of compounds that satisfy this requirement. One strategy for circumventing this problem is to utilize stable precursor molecules that form the active doping complex in situ during the doping process or in a postdeposition thermal- or photo-activation step. Some of us have reported on the use of 1H-benzimidazole (DMBI) and benzimidazolium (DMBI-I) salts as solution- and vacuum-processable n-type dopant precursors, respectively. It was initially suggested that DMBI dopants function as single-electron radical donors wherein the active doping species, the imidazoline radical, is generated in a postdeposition thermal annealing step. Herein we report the results of extensive mechanistic studies on DMBI-doped fullerenes, the results of which suggest a more complicated doping mechanism is operative. Specifically, a reaction between the dopant and host that begins with either hydride or hydrogen atom transfer and which ultimately leads to the formation of host radical anions is responsible for the doping effect. The results of this research will be useful for identifying applications of current organic n-doping technology and will drive the design of next-generation n-type dopants that are air stable and capable of doping low-electron-affinity host materials in organic devices.

Kinetics of C(2α)-proton abstraction from 2-benzylthiazolium salts leading to enamines relevant to catalysis by thiamin-dependent enzymes

The kinetics of proton transfer from the C(2α) position of 2-(1-methoxybenzyl)thiazolium salts was studied for the p-H and p-N(CH3)3+ derivatives as models for the protonation of the enamine/C(2α)-carbanion, a key intermed