19611-80-4

Upstream product

• 52190-18-8 2-(1H-indol-3-yl)-N-phenyl acetamide 
• 526-55-6 2-(3-indole)-ethanol 
• 62-53-3 aniline 
• 108-86-1 bromobenzene 
• 61-54-1 tryptamine 
• 108-95-2 phenol 
• 591-50-4 iodobenzene 
• 22980-09-2 indolyl-3-glyoxylyl chloride 
• 120-72-9 indole 
• 73031-16-0 2-(1H-indol-3-yl)-2-oxo-N-phenylacetamide 
• 108-94-1 cyclohexanone 
• 79-37-8 oxalyl dichloride 
• 29745-09-3 N-(2-(1H-indol-3-yl)ethyl)pyridine-2-carboxamide 
• 98-80-6 phenylboronic acid 

Downstream Products

• 1366416-62-7 C₁₉H₂₀N₂ 
• 1366416-27-4 N-allyl-N-phenyltryptamine 

Relevant academic research and scientific papers

Copper Catalyzed C-N Cross-Coupling Reaction of Aryl Boronic Acids at Room Temperature through Chelation Assistance

A copper-catalyzed selective C-N cross-coupling has been developed based on chelation-assisted amidation of readily available aryl boronic acids at room-temperature under open-flask conditions. The reaction is scalable and tolerates a wide spectrum of functional groups delivering fully substituted unsymmetrical amides in high yields (up to 96%). The C-N cross coupling also established with aryl silanes, extending the palette of coupling partners of this strategy.

METHOD FOR PRODUCING AROMATIC AMINE COMPOUNDS FROM PHENOLS

PROBLEM TO BE SOLVED: To provide a method for producing an aromatic amine compound from phenols and amines with a high yield and a high selectivity, which includes ones subjected to polyfunctionalization, under relatively low temperature and relatively low pressure, without using an additive which gives a co-product having high environmental load. SOLUTION: Phenols and hydrogen are introduced into a first catalyst cartridge receiving a solid catalyst containing platinum group elements and continuously hydrogenated into cyclohexanones. The resultant cyclohexanones, along with amines selected from ammonia, primary amines and secondary amines, and hydrogen trapping agents are subsequently introduced into a second catalyst cartridge receiving a solid catalyst containing platinum group elements to continuously produce aromatic amine compounds by dehydration condensation and dehydrogenation with amines. SELECTED DRAWING: Figure 2 COPYRIGHT: (C)2021,JPOandINPIT

Minimization of Back-Electron Transfer Enables the Elusive sp3 C?H Functionalization of Secondary Anilines

Anilines are some of the most used class of substrates for application in photoinduced electron transfer. N,N-Dialkyl-derivatives enable radical generation α to the N-atom by oxidation followed by deprotonation. This approach is however elusive to monosubstituted anilines owing to fast back-electron transfer (BET). Here we demonstrate that BET can be minimised by using photoredox catalysis in the presence of an exogenous alkylamine. This approach synergistically aids aniline SET oxidation and then accelerates the following deprotonation. In this way, the generation of α-anilinoalkyl radicals is now possible and these species can be used in a general sense to achieve divergent sp3 C?H functionalization.

Fe-Catalyzed Pictet-Spengler-Type Cyclization via Selective Four-Electron Reductive Functionalization of CO2

Herein, we describe a novel catalytic Pictet-Spengler-type cyclization using CO2 as a nontoxic and sustainable C1 feedstock with environmentally benign and non-precious-metal iron as catalyst. The reaction is achieved by selective four-electron reduction of CO2 into methylene level intermediate through carefully tuning the reaction parameters. A variety of tetrahydro-β-carbolines and other nitrogen-containing heterocycles can be easily obtained under mild conditions. Mechanistic studies have shown that tetrahydro-β-carbolines are probably obtained via spiroindolenine intermediates.

In water alkylation of amines with alcohols through a borrowing hydrogen process catalysed by ruthenium nanoparticles

A simple and environmentally benign procedure for the synthesis of secondary amines in water has been developed. Combining Ru3(CO)12, tetraphenylcyclopentadienone and a small quantity of TGPS-750-M surfactant, primary and secondary alcohols were alkylated at N employing equimolar amounts of aromatic amines in water. The reaction occurs under microwave (MW) dielectric heating with high conversion and high yield. When required, the use of biomass-derived 2-MeTHF or GVL as a co-solvent is possible. Under the influence of MWs, a Ru nanoparticle-nanomicelle combination was formed acting as an effective and recyclable catalyst. This protocol was also employed for "in water" cyclisation to synthesise biologically relevant pyrrolobenzodiazepines (PBDs).

Continuous Synthesis of Aryl Amines from Phenols Utilizing Integrated Packed-Bed Flow Systems

Aryl amines are important pharmaceutical intermediates among other numerous applications. Herein, an environmentally benign route and novel approach to aryl amine synthesis using dehydrative amination of phenols with amines and styrene under continuous-flow conditions was developed. Inexpensive and readily available phenols were efficiently converted into the corresponding aryl amines, with small amounts of easily removable co-products (i.e., H2O and alkanes), in multistep continuous-flow reactors in the presence of heterogeneous Pd catalysts. The high product selectivity and functional-group tolerance of this method allowed aryl amines with diverse functional groups to be selectively obtained in high yields over a continuous operation time of one week.

“On Water” promoted N-arylation reactions using Cu (0)/myo-inositol catalytic system

Myo-inositol is originally applied as a cardiovascular medicine in clinic, which can be multi-ton manufactured via extraction from the byproducts in agricultural product processing such as defatted rice bran and corn-soaking water. Herein, the application of myo-inositol (MI) as a novel versatile tridentate O-donor ligand has been first described for promoting Cu-catalyzed amination reaction in aqueous medium.

Pd/Cu Cocatalyzed Oxidative Tandem C-H Aminocarbonylation and Dehydrogenation of Tryptamines: Synthesis of Carbolinones

The Pd/Cu cocatalyzed oxidative tandem C-H aminocarbonylation and dehydrogenation was developed, affording carbolinones with molecular oxygen as the terminal oxidant. Natural product strychnocarpine and its derivatives were prepared conveniently using this strategy.

BippyPhos: A single ligand with unprecedented scope in the Buchwald-Hartwig amination of (hetero)aryl chlorides

Over the past two decades, considerable attention has been given to the development of new ligands for the palladium-catalyzed arylation of amines and related NH-containing substrates (i.e., Buchwald-Hartwig amination). The generation of structurally diverse ligands, by research groups in both academia and industry, has facilitated the accommodation of sterically and electronically divergent substrates including ammonia, hydrazine, amines, amides, and NH heterocycles. Despite these achievements, problems with catalyst generality persist and access to multiple ligands is necessary to accommodate all of these NH-containing substrates. In our quest to address this significant limitation we identified the BippyPhos/[Pd(cinnamyl)Cl]2 catalyst system as being capable of catalyzing the amination of a variety of functionalized (hetero)aryl chlorides, as well as bromides and tosylates, at moderate to low catalyst loadings. The successful transformations described herein include primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, thus demonstrating the largest scope in the NH-containing coupling partner reported for a single Pd/ligand catalyst system. We also established BippyPhos/ [Pd(cinnamyl)Cl]2 as exhibiting the broadest demonstrated substrate scope for metal-catalyzed cross-coupling of (hetero)aryl chlorides with NH indoles. Furthermore, the remarkable ability of BippyPhos/[Pd(cinnamyl)Cl] 2 to catalyze both the selective monoarylation of ammonia and the N-arylation of indoles was exploited in the development of a new one-pot, two-step synthesis of N-aryl heterocycles from ammonia, ortho- alkynylhalo(hetero)arenes and (hetero) aryl halides through tandem N-arylation/hydroamination reactions. Although the scope in the NH-containing coupling partner is broad, BippyPhos/[Pd(cinnamyl)Cl]2 also displays a marked selectivity profile that was exploited in the chemoselective monoarylation of substrates featuring two chemically distinct NH-containing moieties.

Synthesis of tetrahydro-β-carbolines via isomerization of N-allyltryptamines: A metal-catalyzed variation on the Pictet-Spengler theme

An efficient and broadly applicable alternative to the classical Pictet-Spengler synthesis of tetrahydro-β-carbolines is presented. The method relies on metal-catalyzed isomerization of allylic amines to form reactive iminium intermediates which can be trapped by a tethered indole nucleophile. The Royal Society of Chemistry 2012.