106745-67-9

Upstream product

• 1859-70-7 N-(2-acetylphenyl)-4-methylbenzenesulfonamide 
• 1779-49-3 Methyltriphenylphosphonium bromide 
• 551-93-9 2-aminoacetophenone 
• 98-59-9 p-toluenesulfonyl chloride 
• 60249-97-0 1-(1-methylethenyl)-2-nitrobenzene 
• 52562-19-3 2-isopropenylaniline 

Downstream Products

• 133363-66-3 N--N-<2-(methylthio)acetyl>-p-toluenesulfonamide 
• 445235-53-0 N-[2-(1-bromomethyl-vinyl)-phenyl]-4-methyl-benzenesulfonamide 
• 402822-86-0 N-but-3-enyl-N-(2-isopropenyl-phenyl)-4-methyl-benzenesulfonamide 
• 36797-43-0 3-methyl-N-(p-toluenesulfonyl)indole 
• 177763-08-5 3-Methylene-1-(toluene-4-sulfonyl)-2,3-dihydro-1H-indole 
• 402822-74-6 N-allyl-4-methyl-N-(2-(prop-1-en-2-yl)phenyl)benzenesulfonamide 

Relevant academic research and scientific papers

Experimental and Computational Studies on Cp*CyRh(III)/KOPiv-Catalyzed Intramolecular Dehydrogenative Cross-Couplings for Building Eight-Membered Sultam/Lactam Frameworks

Described herein is an unusual Cp*CyRh(III)-catalyzed intramolecular site-specific aryl C-H annulation, a highly chemoselective protocol providing direct access to eight-membered sultams/lactams with broad substrate/functional group tolerance. Experimental and computational studies reveal that such a transformation involves a unique PivOH-assisted aryl C-H activation/alkene insertion/β-H elimination/hydrogen-transfer process involving the Rh(III)-hydride species as the active intermediate with the concomitant release of H2 as the major byproduct, thus enabling the developed Cp*CyRh(III) catalysis with redox-neutral and highly atom-economical features.

Construction of quaternary carbon center by the reaction of aza-o-quinone methide mediated carbocation intermediate

Reactions of carbocationic intermediate corresponding to aza-o-quinone methide with indoles to construct quaternary carbon center were described. Treatment of N-tosylated 2-(2-aminophenyl)propan-2-ol with iron(III) chloride provided tertiary benzylic carbocation intermediate possible to isomerize to the corresponding aza-o-quinone methide. The electron-deficient intermediate enabled to undergo nucleophilic attack by indoles, representing the first example of intermolecular formation of quaternary carbon center using aza-o-quinone methide mediated carbocation intermediate.

Cobalt-catalyzed cyclization with the introduction of cyano, acyl and aminoalkyl groups

An efficient synthesis of carbo-and heterocycles using CC, CO and CN bonds under cobalt catalysis is described. The substituents on olefins are key for controlling the regio-and chemoselectivity in the initial hydrogen atom transfer step and quaternary carbons are efficiently constructed under mild conditions. Cyclopropane cleavage and tandem cyclization give highly functionalized bicyclic skeletons in a single operation.

Pd-tBuONO Cocatalyzed Aerobic Indole Synthesis

A Pd-tBuONO co-catalyzed scalable and practical synthesis of indoles with molecular oxygen as terminal oxidant is developed. Either terminal or internal 2-vinylanilines could be smoothly converted to desired indoles under one general condition. This method has been evaluated in the large scale synthesis of indomethacin and a potential anti-breast cancer drug candidate 1. (Figure presented.).

Copper-catalyzed synthesis of N-aryl and N-sulfonyl indoles from 2-vinylanilines with O2 as terminal oxidant and TEMPO as cocatalyst

A copper-catalyzed intramolecular alkene oxidative amination that utilizes TEMPO as cocatalyst and O2 as the terminal oxidant has been developed. The method furnishes N-aryl and N-sulfonyl indoles from N-aryl and N-sulfonyl 2-vinylanilines, res

Silver(I)-mediated C-H amination of 2-alkenylanilines: Unique solvent-dependent migratory aptitude

A highly effective silver(I)-mediated C-H amination of 2-alkenylanilines has been developed to afford a diverse range of substituted indoles. High functional group tolerance, broad substrate scope, simple/fast/high-yielding reaction, and recovery/reuse of the inexpensive silver oxidant are noteworthy. Furthermore, an uncommon migratory process of β-monosubstituted 2-alkenylanilines with solvent-dependence was demonstrated.

Intramolecular aminocyanation of alkenes by N-CN bond cleavage

A metal-free, Lewis acid promoted intramolecular aminocyanation of alkenes was developed. B(C6F5)3 activates N-sulfonyl cyanamides, thus leading to a formal cleavage of the N-CN bonds in conjunction with vicinal addition o

Copper-catalyzed oxidative amination and allylic amination of alkenes

Enamines and enamides are useful synthetic intermediates and common components of bioactive compounds. A new protocol for their direct synthesis by a net alkene C-H amination and allylic amination by using catalytic Cu II in the presence of MnO2 is reported. Reactions between N-aryl sulfonamides and vinyl arenes furnish enamides, allylic amines, indoles, benzothiazine dioxides, and dibenzazepines directly and efficiently. Control experiments further showed that MnO2 alone can promote the reaction in the absence of a copper salt, albeit with lower efficiency. Mechanistic probes support the involvement of nitrogen-radical intermediates. This method is ideal for the synthesis of enamides from 1,1-disubstituted vinyl arenes, which are uncommon substrates in existing oxidative amination protocols. A new protocol for the direct synthesis of enamides and allylic amines by oxidative N-H/C-H coupling of N-sulfonylanilines with vinylarenes is presented. The reaction works in both inter- and intramolecular modes and is catalyzed by copper salts by using MnO2 as the stoichiometric oxidant (see scheme). Nitrogen heterocycles including indoles, benzothiazine dioxides, and dibenzazepines can be formed. Copyright

Novel formation of indoles and 3,1-benzoxazines from o-alkenylanilides and dimethyl(methylthio)sulfonium trifluoromethanesulfonate

The reaction of dimethyl(methylthio)sulfonium trifluoromethanesulfonate (DMTST) with o-allylphenol gave 2-methylthiomethyl-2,3-dihydrobenzofuran in 97% yield. The reaction of DMTST with N-tosyl-o-isopropenylanilide followed by the addition of aq sodium carbonate afforded N-tosyl-3-methylindole in 88% yield, whereas N-tosyl-o-vinylanilide afforded N-tosylindoline in 85% yield.

A novel synthesis of substituted quinolines using ring-closing metathesis (RCM): Its application to the synthesis of key intermediates for anti-malarial agents

A method for synthesizing substituted quinolines using ruthenium-catalyzed ring-closing metathesis as a key step has been developed. Substituted 1,2-dihydroquinolines, 4-silyloxy-1,2-dihydroquinoline and 4-methoxy-1,2- dihydroquinoline, were successfully synthesized in excellent yields via ene-ene metathesis and silyl or alkyl enol ether-ene metathesis, respectively. The synthetic intermediates of the antimalarial agents quinine, chloroquine, and PPMP-quinine hybrid were efficiently synthesized by this methodology.