14454-14-9

Upstream product

• 636-98-6 p-nitrobenzene iodide 
• 540-37-4 p-aminoiodobenzene 

Downstream Products

• 110606-23-0 N-p-iodophenyl-2-furylacrylohydroxamic acid 
• 13125-93-4 1-iodo-4-nitrosobenzene 
• 1360771-78-3 C₁₃H₉I₂NO₂ 
• 175278-18-9 N-(4-bromo-2-(trifluoromethoxy)phenyl)acetamide 
• 67274-48-0 N-acetyl-N-(4-bromophenyl)hydroxylamine 
• 874814-76-3 N-(4-iodo-2-(trifluoromethoxy)phenyl)acetamide 
• 96127-01-4 N-Hydroxy-N-(4-iodo-phenyl)-benzamide 
• 330195-72-7 methyl 5-iodo-1H-indole-3-carboxylate 
• 1396396-19-2 ethyl 2-benzoyl-1-(4-iodophenyl)-5-phenyl-1H-pyrrole-3-carboxylate 

Relevant academic research and scientific papers

Synthesis and preliminary evaluation of a library of polycyclic small molecules for use in chemical genetic assays

(-)-Shikimic acid, 3, was converted into both enantiomers of epoxycyclohexenol carboxylic acid, 7, which were attached to a solid support via a photocleavable linker. Tandem acylation-1,3-dipolar cycloaddition with nitrones 11a-g yielded tetracyclic templates 12a-g. After development of several efficient coupling reactions of iodobenzyl tetracycles 12b-d and completion of extensive validation protocols, a splitpool synthesis yielded a binary encoded library calculated to contain 2.18 million polycyclic compounds. These compounds are compatible with miniaturized cell-based 'forward' chemical genetic assays designed to explore biological pathways and 'reverse' chemical genetic assays designed to explore protein function. As a simple illustration of the potential of these compounds, several were shown to activate a TGF-β-responsive reporter gene in mammalian cells.

Polystyrene stabilized iridium nanoparticles catalyzed chemo- and regio-selective semi-hydrogenation of nitroarenes to N-arylhydroxylamines

Polystyrene stabilized Iridium (Ir@PS) nanoparticles (NPs) as a heterogeneous catalyst have been developed and characterized by IR, UV–Vis, SEM, TEM, EDX and XRD studies. The prepared Ir@PS catalyst showed excellent reactivity for chemo- and regio-selective controlled-hydrogenation of functionalized nitroarenes to corresponding N-arylhydroxylamine using hydrazine hydrate as reducing source and environmentally benign polyethylene glycol (PEG-400) as green solvent. The present methodology was applied for vast substrate scope and found to be compatible with wide range of reducible functional groups. The reaction performed at 85 °C or ambient temperature and completed within 5–80 minutes. The catalyst can easily be filtered out from reaction mixture and reusable.

Practical bromination of arylhydroxylamines with SOBr2 towards ortho-bromo-anilides

A facile approach for synthesizing ortho-bromoanilides from readily available aryhydroxylamines and thionyl bromide is demonstrated in this work. Mild reaction conditions and broad scope of substrates ranging from heterocyclic structures to pharmaceutics-potential motifs are used in the reactions of this paper. Efficient bromination of ortho C–H bonds of the aryhydroxylamines has been achieved. Ortho-bromoanilide products were obtained in good to excellent yields, and model scaled-up reactions of this synthetic approach are shown in this work.

A general and scalable synthesis of polysubstituted indoles

A consecutive 2-step synthesis of N-unprotected polysubstituted indoles bearing an electron-withdrawing group at the C-3 position from readily available nitroarenes is reported. The protocol is based on the [3,3]-sigmatropic rearrangement of N-oxyenamines generated by the DABCO-catalyzed reaction of N-arylhydroxylamines and conjugated terminal alkynes, and delivers indoles endowed with a wide array of substitution patterns and topologies.

Bi(I)-Catalyzed Transfer-Hydrogenation with Ammonia-Borane

A catalytic transfer-hydrogenation utilizing a well-defined Bi(I) complex as catalyst and ammonia-borane as transfer agent has been developed. This transformation represents a unique example of low-valent pnictogen catalysis cycling between oxidation states I and III, and proved useful for the hydrogenation of azoarenes and the partial reduction of nitroarenes. Interestingly, the bismuthinidene catalyst performs well in the presence of low-valent transition-metal sensitive functional groups and presents orthogonal reactivity compared to analogous phosphorus-based catalysis. Mechanistic investigations suggest the intermediacy of an elusive bismuthine species, which is proposed to be responsible for the hydrogenation and the formation of hydrogen.

Synthesis of N-aryl and N-heteroaryl hydroxylamines via partial reduction of nitroarenes with soluble nanoparticle catalysts

Polystyrene-supported ruthenium nanoparticles enable the selective hydrazine-mediated reduction of nitroarenes to hydroxylamine products in high yield and selectivity. Key to obtaining the hydroxylamine product in good yield was the use of organic solvents capable of solubilizing the polystyrene-supported nanoparticle catalyst. N-aryl and N-heteroaryl hydroxylamines are generated under exceptionally mild conditions and in the presence of a various easily reduced functional groups.

Visible-Light, Photoredox-Mediated Oxidative Tandem Nitroso-Diels–Alder Reaction of Arylhydroxylamines with Conjugated Dienes

Arylhydroxylamines were used in the nitroso-Diels–Alder reaction to generate in situ nitrosoarenes under visible-light, catalytic and aerobic conditions. Mixing a solution of aryl- or heteroarylhydroxylamines with conjuguated dienes in the presence of a catalytic amount of Ru(bpy)3Cl2 afforded 3,6-dihydro-1,2-oxazines in good yields under an oxygen atmosphere.

Hydroxamic Acids as Chemoselective (ortho-Amino)arylation Reagents via Sigmatropic Rearrangement

The use of readily available hydroxamic acids as reagents for the chemoselective (ortho-amino)arylation of amides is described. This reaction proceeds under metal-free, mild conditions, displays a very broad scope, and constitutes a direct approach for the metal-free attachment of aniline residues to carbonyl derivatives.

TRIFLUOROMETHOXYLATION OF ARENES VIA INTRAMOLECULAR TRIFLUOROMETHOXY GROUP MIGRATION

The present invention provides a process of producing a trifluoromethoxylated aryl or trifluoromethoxylated heteroaryl having the structure: (I), wherein A is an aryl or heteroaryl, each with or without subsutitution; and R1 is -H, -(alkyl), -(alkenyl), -(alkynyl), -(aryl), -(heteroaryl), - (alkylaryl), - (alkylheteroaryl), -NH-(alkyl), -N(alkyl)2, -NH-(alkenyl), -NH-(alkynyl) -NH-(aryl), -NH-(heteroaryl), -O-(alkyl), -O-(alkenyl), -O-(alkynyl), -O-(aryl), -O-(heteroaryl), -S-(alkyl), -S- (alkenyl), -S-(alkynyl), -S-(aryl), or -S-(heteroaryl), comprising: (a) reacting a compound having the structure: (II), with a trifluoromethylating agent in the presence of a base in a first suitable solvent under conditions to produce a compound having the structure: (III); and (b) maintaining the compound produced in step (a) in a second suitable solvent under conditions sufficient to produce the trifluoromethoxylated aryl or trifluormethoxylated heteroaryl having the structure: (I).

Mechanistic studies on intramolecular C-H trifluoromethoxylation of (hetero)arenes via OCF3-migration

The one-pot two-step intramolecular aryl and heteroaryl C-H trifluoromethoxylation recently reported by our group has provided a general, scalable, and operationally simple approach to access a wide range of unprecedented and valuable OCF3-containing building blocks. Herein we describe our investigations to elucidate its reaction mechanism. Experimental data indicate that the O-trifluoromethylation of N-(hetero)aryl-N-hydroxylamine derivatives is a radical process, whereas the OCF3-migration step proceeds via a heterolytic cleavage of the N-OCF3 bond followed by rapid recombination of a short-lived ion pair. Computational studies further support the proposed ion pair reaction pathway for the OCF3-migration process. We hope that the current study would provide useful insights for the development of new transformations using versatile N-(hetero)aryl-N-hydroxylamine synthons.