5257-06-7

Usage

Synthesis Reference(s)

Chemical and Pharmaceutical Bulletin, 36, p. 462, 1988 DOI: 10.1248/cpb.36.462

InChI:InChI=1/C9H9NO2/c1-7(12)8-4-2-3-5-9(8)10-6-11/h2-6H,1H3,(H,10,11)

Upstream product

• 83-34-1 3-Methylindole 
• 93-59-4 Perbenzoic acid 
• 67-66-3 chloroform 
• 64-18-6 formic acid 
• 551-93-9 2-aminoacetophenone 
• 87-51-4 indole-3-acetic acid 
• 4375-15-9 3-methyl-2,3-dihydro-1H-indole 
• 1188-33-6 N,N-dimethylformamide diethyl diacetal 
• 16714-26-4 1-(2-azido-phenyl)-ethanone 
• 2142-69-0 2-bromophenyl methyl ketone 
• 77287-34-4 formamide 
• 100-46-9 benzylamine 
• 645-56-7 4-n-Propylphenol 
• 577-59-3 2-acetylnitrobenzene 

Downstream Products

• 700-46-9 4-methylquinazoline 
• 89937-02-0 N-[2-(1-Hydroxy-1-methyl-ethyl)-phenyl]-formamide 
• 89937-01-9 N-[2-(1-Hydroxy-1-methyl-propyl)-phenyl]-formamide 
• 491-35-0 C₆H₄NCH₂CHCCH₂ 
• 83-34-1 3-Methylindole 
• 551-93-9 2-aminoacetophenone 
• 49666-80-0 o-Aminoacetophenon-ω-sulfonsaeure 
• 169775-79-5 N-[2-(1-Hydroxy-1,3-dimethyl-but-2-enyl)-phenyl]-formamide 
• 169775-78-4 N-[2-((E)-1-Hydroxy-1-methyl-3-phenyl-allyl)-phenyl]-formamide 
• 6637-33-8 2-(2'-aminophenyl)-4-methylquinoline 
• 529-37-3 4(1H)-quinolinone 
• 521270-78-0 1-(2-isocyanophenyl)ethan-1-one 
• 5465-86-1 ML 204 
• 4789-76-8 4-methyl-2-phenylquinoline 

Relevant academic research and scientific papers

Photooxidation of tryptophan leading to 2-Aminoacetophenone - A possible reason for the untypical aging off-flavor in wine

2-Aminoacetophenone (AAP) was recognized as the key compound for the so-called untypical aging off-flavor (UTA) in Vitis vinifera wines. In this study, it was shown that AAP can be formed by photooxidation of free and protein-bound tryptophan (TRP) in combination with a subsequent storage in model wine. Solutions of TRP and lysozyme were exposed to artificial sunlight both in the presence and in the absence of the photosensitizer riboflavin. Aliquots of the irradiation batches were stored in model wine solutions containing tartaric acid, sulfite and ethanol in different combinations. AAP formation could be identified from both free and bound (lysozyme) TRP, while free TRP resulted in higher yields. The presence of riboflavin during irradiation generally favored the AAP formation. AAP formation increased with increasing irradiation times, but AAP was not detectable, if TRP was directly incubated in model wine. Not only the irradiation time but also the storage time of model wines favored the formation of AAP. Concerning the model wine composition, it became evident that the presence of tartaric acid resulted in the highest AAP formation during storage.

A three-component iodine-catalyzed oxidative coupling reaction: a heterodifunctionalization of 3-methylindoles

A metal-free method for the synthesis of heterodifunctional indole derivatives is developed through TBHP/KI-mediated oxidative coupling. The reaction constructs C-O and C-C bonds in succession with the help oftert-butyl peroxy radicals generated by the TBHP/KI catalytic system, enabling the direct realization of the heterodifunctionalization of indole in one pot. The product of this reaction is a novel heterodifunctional compound. This work might provide a new effective method for the synthesis of polycyclic indole compounds.

Photocatalytic Oxidative C-C Bond Cleavage of the Pyrrole Ring in 3-Methylindole induced by Colloidal CdS Particles

Binding of 3-methylindole (3-MI) to the surface of colloidal CdS particles modifies their luminescence Behaviour so that the trapped electron and hole generated upon photoirradiation are scavenged by adsorbed O2 and 3-MI to yield 2-acetylformanilide and 2-aminoacetopnenone.

Oxidative Cleavage of Indoles Mediated by Urea Hydrogen Peroxide or H2O2 in Polar Solvents

The oxidative cleavage of indoles (Witkop oxidation) involving the use of H2O2 or urea hydrogen peroxide in combination with a polar solvent has been described. Among these solvents, 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) stands out as the one affording the corresponding 2-ketoacetanilides generally in higher yields The protocol described has also enabled the oxidation of different pyrroles and furans derivatives. Furthermore, the procedure was implemented in a larger-scale and HFIP was distilled from the reaction mixture and reused (up to 4 cycles) without a significant detriment in the reaction outcome, which remarks its sustainability and applicability. (Figure presented.).

Organic photoredox catalyzed C-H silylation of quinoxalinones or electron-deficient heteroarenes under ambient air conditions

Direct C-H silylation of quinoxalinones was achieved by the combination of organic photoredox catalysis and hydrogen atom transfer (HAT) under ambient air conditions. Transition metal- and external oxidant-free conditions were the major features of this protocol. A series of silylated quinoxalinones with broad functional groups had been synthesized in moderate to high yields. This methodology was also applicable for the C-H silylation of some electron-deficient heteroarenes.

Auto-tandem PET and EnT photocatalysis by crude chlorophyll under visible light towards the oxidative functionalization of indoles

Chlorophyll is the most abundant photocatalytic pigment that enables plants to absorb solar energy and convert it to energy storage molecules. Herein, we report a tandem photocatalytic approach utilizing the natural pigment chlorophyll in crude form to achieve photoinduced electron transfer (PET) and energy transfer (EnT) towards the oxidative functionalization of indoles. Redox potentials, ESR, fluorescence quenching and UV experiments have evidenced the dual catalytic activity of chlorophyll. The highlight of the study is the auto-tandem photocatalytic role of chlorophyll to enable the green oxidation of indoles using molecular oxygen as the oxidant, water as the reaction medium, and photochemical energy from the visible region of the spectrum.

Solvent-Dependent Cyclization of 2-Alkynylanilines and ClCF2COONa for the Divergent Assembly of N-(Quinolin-2-yl)amides and Quinolin-2(1 H)-ones

Herein, we present an expedient Cu-catalyzed [5 + 1] cyclization of 2-alkynylanilines and ClCF2COONa to divergent construction of N-(quinolin-2-yl)amides and quinolin-2(1H)-ones by regulating the reaction solvents. Notably, nitrile acts as a solvent and performs the Ritter reactions. ClCF2COONa is used as a C1 synthon in this transformation, which also represents the first example for utilization of ClCF2COONa as an efficient desiliconization reagent. The current protocol involves in situ generation of isocyanide, copper-activated alkyne, Ritter reaction and protonation.

Selective Oxidative Cleavage of 3-Methylindoles with Primary Amines Affording Quinazolinones

A selective functionalization of C-C-C bonds toward N-C-O bonds is realized by an n-Bu4NI-catalyzed reaction of 3-methylindoles with primary amines using TBHP as the unique oxidant. The systematic process involves oxygenation, nitrogenation, ring-opening, and recyclization, affording a broad range of quinazolinones in good to excellent yields.

Visible-Light-Mediated Dearomatisation of Indoles and Pyrroles to Pharmaceuticals and Pesticides

Dearomatisation of indole derivatives to the corresponding isatin derivatives has been achieved with the aid of visible light and oxygen. It should be noted that isatin derivatives are highly important for the synthesis of pharmaceuticals and bioactive compounds. Notably, this chemistry works excellently with N-protected and protection-free indoles. Additionally, this methodology can also be applied to dearomatise pyrrole derivatives to generate cyclic imides in a single step. Later this methodology was applied for the synthesis of four pharmaceuticals and a pesticide called dianthalexin B. Detailed mechanistic studies revealed the actual role of oxygen and photocatalyst.

Modeling Tryptophan/Indoleamine 2,3-Dioxygenase with Heme Superoxide Mimics: Is Ferryl the Key Intermediate?

Tryptophan oxidation in biology has been recently implicated in a vast array of paramount pathogenic conditions in humans, including multiple sclerosis, rheumatoid arthritis, type-I diabetes, and cancer. This 2,3-dioxygenative cleavage of the indole ring of tryptophan with dioxygen is mediated by two heme enzymes, tryptophan 2,3-dioxygenase (TDO) and indoleamine 2,3-dioxygenase (IDO), during its conversion to N-formylkynurenine in the first and rate-limiting step of kynurenine pathway. Despite the pivotal significance of this enzymatic transformation, a vivid viewpoint of the precise mechanistic events is far from complete. A heme superoxide adduct is thought to be the active oxidant in both TDO and IDO, which, following O-O bond cleavage, presumably generates a key ferryl (FeIV=O) reaction intermediate. This study, for the first time in model chemistry, demonstrates the potential of synthetic heme superoxide adducts to mimic the bioinorganic chemistry of indole dioxygenation by TDO and IDO, challenging the widely accepted categorization of these metal adducts as weak oxidants. Herein, an electronically divergent series of ferric heme superoxo oxidants mediates the facile conversion of an array of indole substrates into their corresponding 2,3-dioxygenated products, while shedding light on an unequivocally occurring, putative ferryl intermediate. The oxygenated indole products have been isolated in a?31% yield, and characterized by LC-MS, 1H and 13C NMR, and FT-IR methodologies, as well as by 18O2(g) labeling experiments. Distinctly, the most electron-deficient superoxo adduct is observed to react the fastest, specifically with the most electron-rich indole substrate, underscoring the cruciality of electrophilicity of the heme superoxide moiety in facilitating the initial indole activation step. Comprehensive understanding of such mechanistic subtleties will benefit future attempts in the rational design of salient therapeutic agents, including next generation anticancer drug targets with amplified effectivity.