71017-85-1

Upstream product

• 448-61-3 2,4,6-triphenylpyrylium tetrafluoroborate 
• 104-86-9 4-chlorobenzylamine 
• 771579-40-9 4-chloromethyl-benzylamine 

Downstream Products

• 29865-54-1 1-(4'-chlorophenyl)-2-nitropropane 
• 5216-35-3 1,2-bis(4-chlorophenyl)ethane 
• 873-76-7 para-Chlorobenzyl alcohol 
• 131523-32-5 2-(4-chloro-benzyl)-1H-isoindole-1,3(2H)-dione 
• 130745-75-4 2-(4-chlorobenzyl)-1,3-diphenylpropane-1,3-dione 
• 130745-84-5 3-(4-chlorobenzyl)oxy-1,3-diphenyl-2-propen-1-one 
• 61713-41-5 3-(4-chlorobenzyl)pentane-2,4-dione 
• 3602-62-8 3-(4-chlorobenzyloxy)-3-penten-2-one 
• 130745-73-2 2-(4-chlorobenzyl)-1-phenylbutane-1,3-dione 
• 21573-65-9 1-(4-chlorophenyl)hexan-2-one 
• 59305-51-0 1-chloro-4-<(phenylseleno)methyl>benzene 
• 517920-59-1 2-[(4-chlorophenyl)methyl]-4,4,5,5-tetramethyl-1,3,2-dioxaborolane 
• 580-35-8 2,4,6-triphenylpyridine 
• 52497-66-2 α,α-Dimethyl-α-nitro-β-(4-chlorphenyl)-aethan 

Relevant academic research and scientific papers

Metal-free synthesis of unsymmetrical selenides from pyridinium salts and diselenides catalysed by visible light

We report the first metal-free selenolations of pyridinium salts with diselenides to prepare unsymmetrical organoselenides catalysed by visible light. This protocol is an efficient and green method for the preparation of unsymmetrical organoselenides because metal-free conditions and readily accessible diselenides are used.

C-H Alkylation of Aldehydes by Merging TBADT Hydrogen Atom Transfer with Nickel Catalysis

Catalyst controlled site-selective C-H functionalization is a challenging but powerful tool in organic synthesis. Polarity-matched and sterically controlled hydrogen atom transfer (HAT) provides an excellent opportunity for site-selective functionalization. As such, the dual Ni/photoredox system was successfully employed to generate acyl radicals from aldehydes via selective formyl C-H activation and subsequently cross-coupled to generate ketones, a ubiquitous structural motif present in the vast majority of natural and bioactive molecules. However, only a handful of examples that are constrained to the use of aryl halides are developed. Given the wide availability of amines, we developed a cross-coupling reaction via C-N bond cleavage using the economic nickel and TBADT catalyst for the first time. A range of alkyl and aryl aldehydes were cross-coupled with benzylic and allylic pyridinium salts to afford ketones with a broad spectrum of functional group tolerance. High regioselectivity toward formyl C-H bonds even in the presence of α-methylene carbonyl or α-amino/oxy methylene was obtained.

Visible-Light-Induced Deaminative Alkylation/Cyclization of Alkyl Amines with N-Methacryloyl-2-phenylbenzoimidazoles in Continuous-Flow Organo-Photocatalysis

Herein, we present a metal-free visible-light-induced eosin-y-catalyzed deaminative strategy for the sequential alkylation/cyclization of N-methacryloyl-2-phenylbenzoimidazoles with alkyl amine-derived Katritzky salts, which provides an efficient avenue for the construction of various benzo[4,5]imidazo[2,1-a]isoquinolin-6(5H)-one derivatives in moderate to excellent yields under mild reaction conditions. The key enabling feature of this novel reaction includes utilization of redox-active pyridinium salts from abundant and inexpensive primary amine feedstocks that were converted into alkyl radicals via C-N bond scission and subsequent alkylation/cyclization with N-methacryloyl-2-phenylbenzoimidazoles by the formation of two new C-C bonds. In addition, we implemented this protocol for a variety of amino acids, affording the products in moderate yields. Moreover, the novel, environmentally benign batch protocol was further carried out in a continuous-flow regime by utilizing a perfluoroalkoxy alkane tubing microreactor under optimized reaction conditions with a blue light-emitting diode light source, enabling excellent yields and a shorter reaction time (19 min) versus the long reaction time (16 h) of the batch reaction. The reaction displays excellent functional group tolerance, easy operation, scalability, mild reaction conditions, and broad synthetic utility.

Sulfinates from Amines: A Radical Approach to Alkyl Sulfonyl Derivatives via Donor-Acceptor Activation of Pyridinium Salts

Synthetically versatile alkyl sulfinates can be prepared from readily available amines, using Katritzky pyridinium salt intermediates. In a catalyst-free procedure, primary, secondary, and benzylic alkyl radicals are generated by photoinduced or thermally induced single-electron transfer (SET) from an electron donor-acceptor (EDA) complex, and trapped by SO2 to generate sulfonyl radicals. Hydrogen atom transfer (HAT) from Hantzsch ester gives alkyl sulfinate products, which are used to prepare a selection of medicinal chemistry relevant sulfonyl-containing motifs.

Visible Light-Driven α-Alkylation of N-Aryl tetrahydroisoquinolines Initiated by Electron Donor-Acceptor Complexes

The visible light-driven α-alkylation of N-aryl tetrahydroisoquinolines was initiated through electron donor-acceptor complex photochemistry. The reaction can proceed smoothly without the addition of any photocatalysts, transition-metal catalysts, or additional oxidants. The proposed mechanism was supported by various mechanistic studies, and the reactive open-shell alkyl radicals were generally produced from an alkylamine and underwent radical coupling for alkylating a wide range of N-aryl tetrahydroisoquinolines.

Method for difluoroalkylation after fatty amine deamination

The invention discloses a method for difluoroalkylation after fatty amine deamination in the field of organic synthesis. Particularly the method comprises the following steps: by taking simple and easily available fatty amine represented by a formula A as a raw material, reacting the fatty amine with pyranyl tetrafluoroborate represented by a formula B under a heating or room temperature conditionto obtain alkyl pyridinium represented by a formula C; and under the illumination condition, obtaining various difluoroalkyl substituted alkanes, cycloalkanes and derivatives thereof with high yieldby selecting commercially available [Ir(dtbbpy)(ppy)2]PF6 as a catalyst and difluoroenol silyl ether D as a difluoroalkylation reagent. According to the invention, the method is simple and convenientto operate, simple and mild in reaction condition, excellent in functional group compatibility and suitable for large-scale production and synthesis; and fluorine-containing amino acid with potentialapplication value can be obtained through the catalytic synthesis method, and various difluoroalkyl-containing compounds with novel structures and important significance in the fields of medicines, pesticides and materials can be easily obtained through further conversion of the obtained product.

Visible light promoted deaminative difluoroalkylation of aliphatic amines with difluoroenoxysilanes

A visible light promoted deaminative strategy for the difluoroalkylation reaction utilizing pyridinium-activated aliphatic primary amines and difluoroenoxysilane as substrates has been developed. This protocol is characteriazed by its mild reaction conditions and broad substrate scope, which converted a diverse array of amine-containing molecules to the alkyl-CF2COPh products. Moreover, the resulting products can be easily transformed into a vast array of structurally novel and interesting difluoro-containing moieties, therefore providing a facile route for applications in medicinal chemistry and the life sciences. This journal is

Deaminative Borylation of Aliphatic Amines Enabled by Visible Light Excitation of an Electron Donor–Acceptor Complex

A deaminative strategy for the borylation of aliphatic primary amines is described. Alkyl radicals derived from the single-electron reduction of redox-active pyridinium salts, which can be isolated or generated in situ, were borylated in a visible light-mediated reaction with bis(catecholato)diboron. No catalyst or further additives were required. The key electron donor–acceptor complex was characterized in detail by both experimental and computational investigations. The synthetic potential of this mild protocol was demonstrated through the late-stage functionalization of natural products and drug molecules.

The Synthesis and Reactions of Sterically Constrained Pyrylium and Pyridinium Salts

Efficient syntheses are developed for several pyrylium cations with substitution patterns more sterically demanding than 2,4,6-triphenyl and these are examined as reagents for the conversion of primary amino into a leaving group.The 2-mesityl-4,6-diphenyl derivative did not react smoothly with amines.The 2,6-di-t-butyl-4-phenyl-pyrylium cation gave the corresponding pyridinium derivatives, but they resisted nucleophilic attack. 2-t-Butyl-4,6-diphenylpyridinium cations suffer nucleophilic attack with about the same ease as the 2,4,6-triphenyl analogues.Dihydrobenzopyrylium (6) and tetrahydrodibenzoxanthylium cations (7) gave pyridinium cations which underwent much easier nucleophilic attack: thus they alkylate xanthate anion in ethanol solution and acetate anion in acetic acid.