36035-49-1

Upstream product

• 459-59-6 4-fluoro-N-methylaniline 
• 75-36-5 acetyl chloride 
• 201230-82-2 carbon monoxide 
• 403-46-3 4-fluoro-N,N-dimethylaniline 
• 108-24-7 acetic anhydride 
• 579-58-8 N-methyl-(4-acetamido)phenol 
• 371-40-4 4-fluoroaniline 
• 351-83-7 4'-fluoroacetanilide 
• 74-88-4 methyl iodide 

Downstream Products

• 459-59-6 4-fluoro-N-methylaniline 

Relevant academic research and scientific papers

Carbonylation of C?N Bonds in Tertiary Amines Catalyzed by Low-Valent Iron Catalysts

The first iron catalysts able to promote the formal insertion of CO into the C?N bond of amines are reported. Using low-valent iron complexes, including K2[Fe(CO)4], amides are formed from aromatic and aliphatic amines, in the presence of an iodoalkane promoter. Inorganic Lewis acids, such as AlCl3 and Nd(OTf)3, have a positive influence on the catalytic activity of the iron salts, enabling the carbonylation at a low pressure of CO (6 to 8 bars).

Formamide as an Unconventional Amine Protecting Group for PET Radiochemistry

We developed a versatile, rapid, and robust high-yielding radiochemistry-adapted protocol utilizing formamides as masking groups for secondary and tertiary amines. Selective reducing conditions were devised using borane reagents. In this protocol formamid

Thermolysis and radiofluorination of diaryliodonium salts derived from anilines

Aniline-derived diaryliodonium salts were synthesized and functionalized in good to excellent yields by judicious utilization of electron-withdrawing protecting groups. This simple approach opens another route to radiolabeling amino arenes in relatively complex molecules, such as flutemetamol.

An improved catalyst system for the Pd-catalyzed fluorination of (hetero)aryl triflates

The stable Pd(0) species [(1,5-cyclooctadiene)(L·Pd)2] (L = AdBrettPhos) has been prepared and successfully evaluated as a precatalyst for the fluorination of aryl triflates derived from biologically active and heteroaryl phenols, challenging substrates for our previously reported catalyst system. Additionally, this precatalyst activates at room temperature under neutral conditions, generates 1,5-cyclooctadiene as the only byproduct, and leads to overall cleaner reaction profiles.

Oligo(N-aryl glycines): A new twist on structured peptoids

We explore strategies to enhance conformational ordering of N-substituted glycine peptoid oligomers. Peptoids bearing bulky N-alkyl side chains have previously been studied as important examples of biomimetic "foldamer" compounds, as they exhibit a capacity to populate helical structures featuring repeating cis-amide bonds. Substantial cis/trans amide bond isomerization, however, gives rise to conformational heterogeneity. Here, we report the use of N-aryl side chains as a tool to enforce the presence of trans-amide bonds, thereby engendering structural stability. Aniline derivatives and bromoacetic acid are used in the facile solid-phase synthesis of a diverse family of sequence-specific N-aryl glycine oligomers. Quantum mechanics calculations yield a detailed energy profile of the folding landscape and substantiate the hypothesis that the presence of anilide groups establishes a strong energetic preference for trans-amide bonds. X-ray crystallographic analysis and solution NMR studies verify this preference. Molecular modeling indicates that the linear oligomers can adopt helical structures resembling a polyproline type II helix. High resolution structures of macrocyclic oligomers incorporating both N-alkyl and N-aryl glycine units confirm the ability to direct the presence of trans-amide bonds specifically at N-aryl positions. These results are an important step in developing strategies for the rational de novo design of new structural motifs in biomimetic oligopeptoid systems.

Intrinsic and Equilibrium NMR Isotope Shift Evidence for Negative Hyperconjugation

Intrinsic NMR isotope shifts are found at 19F due to CD3 substitution for CH3 in N-methyl- and N,N-dimethyl-4-fluoroaniline and 4-fluoroanisole.These intrinsic shifts demonstrate isotopic perturbation of negative hyperconjugation, in which C-H(D) bonds act as electron acceptors.Comparison with carbocations and a carbanion through the use of a perturbational analysis based on MO calculations supports the hyperconjugative origin of intrinsic long-range isotope shifts.Equilibrium isotope effects on the protonation of anilines, measured through observation of equilibrium NMR isotope shifts, are also consistent with negative hyperconjugation.