348-06-1

Upstream product

• 94-09-7 p-aminoethylbenzoate 
• 13755-29-8 sodium tetrafluoroborate 
• 7632-00-0 sodium nitrite 
• 540-80-7 tert.-butylnitrite 

Downstream Products

• 51460-00-5 4-(2-morpholin-4-yl-5-phenyl-furan-3-ylazo)-benzoic acid ethyl ester 
• 87747-16-8 4-(2,4-Bis-dimethylamino-thiazol-5-ylazo)-benzoic acid ethyl ester 
• 89076-52-8 (E)-2-(4-Ethoxycarbonylphenyl)-1-(5-nitro-2-furyl)ethylene 
• 93-89-0 benzoic acid ethyl ester 
• 6287-86-1 p-ethoxycarbonylbenzaldehyde 
• 73286-83-6 2-tert-Butyl-1-<4-(ethoxycarbonyl)phenylhydrazono>-1H-isoindolium-tetrafluoroborat 
• 78823-37-7 C₁₅H₁₈O₅ 
• 88740-92-5 C₂₂H₂₀N₆O₃ 
• 7335-27-5 ethyl 4-chlorobenzoate 
• 84875-71-8 Sodium; 4-{4-[(4-ethoxycarbonyl-phenyl)-hydrazono]-3-methyl-5-oxo-4,5-dihydro-pyrazol-1-yl}-benzenesulfonate 
• 70303-37-6 C₁₁H₁₅N₃O₃ 
• 1152-30-3 (E)-ethyl 4-styrylbenzoate 
• 99-77-4 ethyl 4-nitrobenzoate 
• 10540-36-0 4'-fluorobiphenyl-4-carboxylic acid ethyl ester 

Relevant academic research and scientific papers

Metal-Free Visible-Light Synthesis of Arylsulfonyl Fluorides: Scope and Mechanism

The first metal-free procedure for the synthesis of arylsulfonyl fluorides is reported. Under organo-photoredox conditions, aryl diazonium salts react with a readily available SO2 source (DABSO) to afford the desired product through simple nucleophilic fluorination. The reaction tolerates the presence of both electron-rich and -poor aryls and demonstrated a broad functional group tolerance. To shed the light on the reaction mechanism, several experimental techniques were combined, including fluorescence, NMR, and EPR spectroscopy as well as DFT calculations.

Modular and Selective Arylation of Aryl Germanes (C?GeEt3) over C?Bpin, C?SiR3 and Halogens Enabled by Light-Activated Gold Catalysis

Selective C (Formula presented.) –C (Formula presented.) couplings are powerful strategies for the rapid and programmable construction of bi- or multiaryls. To this end, the next frontier of synthetic modularity will likely arise from harnessing the coupling space that is orthogonal to the powerful Pd-catalyzed coupling regime. This report details the realization of this concept and presents the fully selective arylation of aryl germanes (which are inert under Pd0/PdII catalysis) in the presence of the valuable functionalities C?BPin, C?SiMe3, C?I, C?Br, C?Cl, which in turn offer versatile opportunities for diversification. The protocol makes use of visible light activation combined with gold catalysis, which facilitates the selective coupling of C?Ge with aryl diazonium salts. Contrary to previous light-/gold-catalyzed couplings of Ar–N2+, which were specialized in Ar–N2+ scope, we present conditions to efficiently couple electron-rich, electron-poor, heterocyclic and sterically hindered aryl diazonium salts. Our computational data suggest that while electron-poor Ar–N2+ salts are readily activated by gold under blue-light irradiation, there is a competing dissociative deactivation pathway for excited electron-rich Ar–N2+, which requires an alternative photo-redox approach to enable productive couplings.

Visible-Light-Mediated Ru-Catalyzed Synthesis of 3-(Arylsulfonyl)but-3-enals via Coupling of α-Allenols with Diazonium Salts and Sulfur Dioxide

The first coupling of α-allenols, sulfur dioxide, and arenediazonium salts is presented. The three-component reaction which is promoted by visible light can be easily accomplished using DABSO as a sulfur dioxide surrogate in the presence of a photoredox catalyst. In this manner, a broad range of electron-rich and electron-deficient aryl substituents are well accommodated in the sulfonylation-rearrangement cascade to afford the 2,2-disubstituted 3-(arylsulfonyl)but-3-enals in reasonable yields. Based on control experiments, a radical mechanism which does imply 1,2-aryl migration has been proposed.

Copper-mediated tandem ring-opening/cyclization reactions of cyclopropanols with aryldiazonium salts: Synthesis of: N -arylpyrazoles

A general method for the synthesis of structurally diverse N-arylpyrazoles from readily available cyclopropanols and aryldiazonium salts is disclosed. The reaction was conducted at room temperature within minutes with a broad substrate scope and excellent regioselectivity.

Fluorosulfonylation of arenediazonium tetrafluoroborates with Na2S2O5 and N-fluorobenzenesulfonimide

A transition-metal-free Sandmeyer-type fluorosulfonylation reaction has been achieved by the three-component reaction of arenediazonium tetrafluoroborates, Na2S2O5, and N-fluorobenzenesulfonimide (NFSI). The reaction proceeds through a radical tandem process, affording various arenesulfonyl fluorides in moderate to high yields. This protocol not only provides a complement to the previous fluorosulfonylation reactions, but also extends the applications of Sandmeyer reaction.

A highly stable, Au/Ru heterobimetallic photoredox catalyst with a [2.2]paracyclophane backbone

We report the synthesis and catalytic application of a highly stable distance-defined Au/Ru heterobimetallic complex. [2.2]Paracyclophane serves as a backbone, holding the two metal centers in a spatial orientation and metal-metal fixed distance. The Au/Ru heterobimetallic complex is highly stable, easily accessible and exhibits promising catalytic activity in a visible-light mediated dual Au/Ru Meyer-Schuster rearrangement.

Copper(I)-promoted trifluoromethylthiolation of arenediazonium salts with AgSCF3

An efficient method for trifluoromethylthiolation of arenediazonium salts has been developed in mild conditions with a stable and convenient AgSCF3. It provides a straightforward and convenient way for the synthesis of trifluoromethylthiolated compound from diazonium salts in moderate to good yields.

Preparation of N-Arylquinazolinium Salts via a Cascade Approach

An easy manipulation method for the preparation of N-arylquinazolinium salts is described from readily available aryldiazonium salts, nitriles, and 2-aminoarylketones in a one-pot operation. This method relies on the in situ generation of the N-arylnitrilium intermediate from the reaction of aryldiazonium salt with nitrile, which undergoes amination/cascade cyclization/aromatization, leading to N-arylquinazolinium salts in excellent yields. Nucleophilic addition of alkoxide to these N-arylquinazolinium salts provides functionalized dihydro-N-arylquinazoline.

Pentafluoroethylation of Arenediazonium Tetrafluoroborates Using On-Site Generated Tetrafluoroethylene

Copper-mediated pentafluoroethylation of arenediazonium tetrafluoroborates with tetrafluoroethylene (TFE) on-site generated from TMSCF3 has been developed as a new method to prepare pentafluoroethyl arenes. The active pentafluoroethylation reagent “CuC2F5” is pre-generated from CuSCN, TFE and CsF, and its generation and further reaction are strongly solvent-dependent. This pentafluoroethylation reaction represents the first example of Sandmeyer-type pentafluoroethylation, which exhibits good functional group tolerance and potential applications for the synthesis of complicated bioactive compounds.

Perylenequinonoid-catalyzed photoredox activation for the direct arylation of (het)arenes with sunlight

Naturally occurring perylenequinonoid pigments (PQPs) have attracted considerable attention owing to their excellent properties of photosensitization. They have been widely investigated as an aspect of photophysics and photobiology. However, their applications in photocatalysis are yet to be explored. We report here that sunlight along with 1 mol% cercosporin, which is one of the perylenequinonoid pigments, catalyzes the direct C-H bond arylation of (het)arenes by a photoredox process with good regioselectivity and broad functional group compatibility. Furthermore, a gram-scale reaction with great conversions of substrates was achieved even by a cercosporin-containing supernatant without organic solvent extraction and purification after liquid fermentation. Thus we set up a bridge between microbial fermentation and organic photocatalysis for chemical reactions in a sustainable, environmentally friendly manner.