19005-56-2

Upstream product

• 288-13-1 NH-pyrazole 
• 92-66-0 4-bromo-1,1'-biphenyl 
• 108-86-1 bromobenzene 
• 1432475-19-8 potassium 4-(1H-pyrazol-1-yl)phenyltrifluoroborate 
• 92-52-4 biphenyl 
• 144432-80-4 2-(biphenyl-4-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 

Downstream Products

• 1632155-71-5 methyl 5-phenyl-2-(1H-pyrazol-1-yl)benzoate 

Relevant academic research and scientific papers

Dehydrogenative Azolation of Arenes in a Microflow Electrochemical Reactor

The electrochemical synthesis of aryl azoles was performed for the first time in a microflow reactor. The reaction relies on the anodic oxidation of the arene partners making these substrates susceptible for C-H functionalization with azoles, thus requiring no homogeneous transition-metal-based catalysts. The synthetic protocol benefits from the implementation of a microflow setup, leading to shorter residence times (10 min), compared to previously reported batch systems. Various azolated compounds (22 examples) are obtained in good to excellent yields.

Photocatalytic C?H Azolation of Arenes Using Heterogeneous Carbon Nitride in Batch and Flow

The functionalization of aryl C(sp2)?H bonds is a useful strategy for the late-stage modification of biologically active molecules, especially for the regioselective introduction of azole heterocycles to prepare medicinally-relevant compounds. Herein, we describe a practical photocatalytic transformation using a mesoporous carbon nitride (mpg-CNx) photocatalyst, which enables the efficient azolation of various arenes through direct oxidation. The method exhibits a broad substrate scope and is amenable to the late-stage functionalization of several pharmaceuticals. Due to the heterogeneous nature and high photocatalytic stability of mpg-CNx, the catalyst can be easily recovered and reused leading to greener and more sustainable routes, using either batch or flow processing, to prepare these important compounds of interest in pharmaceutical and agrochemical research.

Spectroscopic Studies of the Chan-Lam Amination: A Mechanism-Inspired Solution to Boronic Ester Reactivity

We report an investigation of the Chan-Lam amination reaction. A combination of spectroscopy, computational modeling, and crystallography has identified the structures of key intermediates and allowed a complete mechanistic description to be presented, including off-cycle inhibitory processes, the source of amine and organoboron reactivity issues, and the origin of competing oxidation/protodeboronation side reactions. Identification of key mechanistic events has allowed the development of a simple solution to these issues: manipulating Cu(I) → Cu(II) oxidation and exploiting three synergistic roles of boric acid has allowed the development of a general catalytic Chan-Lam amination, overcoming long-standing and unsolved amine and organoboron limitations of this valuable transformation.

Teaching Old Compounds New Tricks: DDQ-Photocatalyzed C?H Amination of Arenes with Carbamates, Urea, and N-Heterocycles

The C?H amination of benzene derivatives was achieved using DDQ as photocatalyst and BocNH2 as the amine source under aerobic conditions and visible light irradiation. Electron-deficient and electron-rich benzenes react as substrates with moderate to good product yields. The amine scope of the reaction comprises Boc-amine, carbamates, pyrazoles, sulfonimides and urea. Preliminary mechanistic investigations indicate arene oxidation by the triplet of DDQ to radical cations with different electrophilicity and a charge transfer complex between the amine and DDQ as intermediate of the reaction.

PHOTOREDOX-CATALYZED DIRECT C-H FUNCTIONALIZATION OF ARENES

The invention generally relates to methods of making substituted arenes via direct C-H amination. More specifically, methods of making para- and ortho-substituted arenes via direct C-H amination are disclosed. This abstract is intended as a scanning tool for purposes of searching in the particular art and is not intended to be limiting of the present invention.

Site-selective arene C-H amination via photoredox catalysis

Over the past several decades, organometallic cross-coupling chemistry has developed into one of the most reliable approaches to assemble complex aromatic compounds from preoxidized starting materials. More recently, transition metal-catalyzed carbon-hydrogen activation has circumvented the need for preoxidized starting materials, but this approach is limited by a lack of practical amination protocols. Here, we present a blueprint for aromatic carbon-hydrogen functionalization via photoredox catalysis and describe the utility of this strategy for arene amination. An organic photoredox-based catalyst system, consisting of an acridinium photooxidant and a nitroxyl radical, promotes site-selective amination of a variety of simple and complex aromatics with heteroaromatic azoles of interest in pharmaceutical research. We also describe the atom-economical use of ammonia to form anilines, without the need for prefunctionalization of the aromatic component.

Ruthenium-catalyzed c-h silylation of 1-arylpyrazole derivatives and fluoride-mediated carboxylation: Use of two nitrogen atoms of the pyrazole Group

Carboxylation of 1-arylpyrazole derivatives was developed using a ruthenium-catalyzed ortho silylation in conjunction with fluoride-mediated carboxylation with carbon dioxide. The two nitrogen atoms of pyrazole play crucial roles in promoting ortho silylation via the formation of a five-membered ruthenacycle and in accelerating aryl anion formation by lowering the electron density of the aromatic ring. Georg Thieme Verlag Stuttgart New York.

Functionalization of organotrifluoroborates via CU-catalyzed C-N coupling reaction

Potassium N-heterobiaryltrifluoroborates were successfully prepared via a selective Cu-catalyzed C-N coupling reaction. The BF3K moiety was well tolerated under the reaction conditions involving CuI and dimethylethylenediamine (DMEDA) in the presence of DMSO. The Pd-catalyzed Suzuki-Miyaura cross couplings of potassium N-heterobiaryltrifluoroborates with bromoarenes were studied to prepare the N-heterotriaryl compounds. Moreover, homocoupling, iodination, and hydroxylation of potassium N-heterobiaryltrifluoroborates provided the corresponding products in high yields.

Ruthenium-catalyzed C-H functionalization of arylpyrazoles: Regioselective acylation with acid chlorides

A ruthenium-catalyzed C-H acylation of arylpyrazoles with a variety of acyl chlorides is described. The acylation reaction exhibits good regioselectivity and both aromatic and aliphatic acyl chlorides can be effectively coupled to the arylpyrazoles at the

IRON-COPPER CO-CATALYZED PROCESS FOR CARBON-CARBON OR CARBON-HETEROATOM BONDING

The present invention relates to a process for creating a Carbon-Carbon bond (C-C) or a Carbon-Heteroatom bond (C -HE) by reacting a compound carrying a leaving group with a nucleophilic compound carrying a carbon atom or a heteroatom (HE) that can substitute for the leaving group, creating a C-C or C-HE bond, wherein the reaction takes place in the presence of an effective quantity of a catalytic system comprising iron and copper.