19871-46-6

Upstream product

• 100-42-5 styrene 
• 938-05-6 dibromamine-B 
• 473-29-0 N,N-Dichlorobenzenesulfonamide 
• 127-52-6 chloramine-B 
• 87301-29-9 N-(phenylsulfonylimino)-phenyl-λ³-iodane 
• 98-10-2 benzenesulfonamide 
• 938-10-3 phenylsulfonyl azide 
• 186581-53-3 diazomethane 
• 13909-34-7 N-benzylidenephenylsulfonamide 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 

Downstream Products

• 98943-90-9 9-<2-((phenylsulfonyl)amino)-1-phenylethyl>-9,10-dihydroanthracene 
• 137152-23-9 N-(3-Methanesulfinyl-1-phenyl-propyl)-benzenesulfonamide 
• 146579-94-4 1-Benzenesulfonyl-3,4-diphenyl-imidazolidin-2-one 
• 1520-42-9 1,1,2-triphenylethane 
• 117583-57-0 N-(2,2-diphenylethyl)benzenesulfonamide 
• 19871-49-9 N-(2-Iodo-2-phenyl-ethyl)-benzenesulfonamide 
• 78826-13-8 1-benzenesulfonyl-2-phenyl-azetidine 
• 108223-54-7 N-(2-phenylallyl)benzenesulfonamide 
• 93985-81-0 N-(2-oxo-2-phenylethyl)benzenesulfonamide 

Relevant academic research and scientific papers

A new generation of terminal copper nitrenes and their application in aromatic C-H amination reactions

Copper nitrene complexes are highly reactive species and are known as intermediates in the copper catalyzed C-H amination. In this study, three novel copper tosyl nitrene complexes were synthesized at low temperatures, stabilized with heteroscorpionate ligands of the bis(pyrazolyl)methane family. The copper nitrenes were obtained by the reaction of a copper(i) acetonitrile complex with SPhINTs in dichloromethane. We show that the ligand design has a major influence on the catalytic activity and the thermal stability of the copper nitrene complex. Not only the choice of the third N donor, but also the substituent in the 5-position of the pyrazolyl moiety, have an impact on the stability. Furthermore, the novel copper nitrene complexes were used for catalytic aziridination of styrenes and C-H amination reactions of aromatic and aliphatic substrates under mild reaction conditions. Even challenging substrates like benzene and cyclohexane were aminated with good yields. The copper nitrene complexes were characterized using UV/Vis spectroscopy, low temperature Evans NMR spectroscopy, density functional theory, domain-based local pair natural orbital coupled cluster calculations (DLPNO-CCSD(T)) and cryo-UHR mass spectrometry.

Transition-Metal-Free Stereospecific Oxidative Annulative Coupling of Indolines with Aziridines

Tandem C-N bond formation for the oxidative annulation of indolines with aziridines is accomplished employing the combination of DDQ and NaOCl at ambient conditions. Optically active aziridine can be coupled with high enantiomeric purity (>99% ee). The substrate scope, stereocontrol with the enantioenriched substrate, and scale-up are the important practical advantages.

Wheel-to-rhomboid isomerization as well as nitrene transfer catalysis of ruthenium-thiolate wheels

A unique ruthenium-thiolate molecular rhomboid (?)-[Ru(SAr)2(CO)2]8, which consists of eight octahedra linked by alternate face- and vertex-sharing, was produced by isomerization of the molecular wheel (○)-[Ru(SAr)2/

Aminochlorination of Alkenes with CFBSA

A novel catalyst-free aminochlorination of alkenes was developed by the direct addition of alkenes to N-chloro-N-fluorobenzenesulfonamide (CFBSA). The reaction produces 2-chloro-3-fluoramino and 3-chloro-2-fluoroamino adducts in 1,2-dichloroethane under reflux and dichloromethane at room temperature, respectively, in a regioselective manner. The electronic and steric effects of the fluorine atom of CFBSA have proven to be crucial for the reactivity and regioselectivity. A variety of transformations have been achieved to form 2-chloroenamines, chloroamines, aziridines and N-phenylbenzenesulfonamides under different conditions. Notably, the N–F bond in the adducts formed could be a useful handle for further transformations to useful compounds in organic synthesis.

Studies on the formal [3 + 2] cycloaddition of aziridines with alkenes for the synthesis of 1-azaspiroalkanes

The Lewis acid-mediated [3 + 2] cycloaddition of N-sulfonyl- and N-sulfamoylaziridines with alkenes provides a rapid and efficient access to 1-azaspiro[4.n]alkanes. Experimental studies have been combined with DFT calculations to explore the mechanism of the reaction. They demonstrate that the nature of the electron-withdrawing nitrogen protecting group has a very limited influence on the course of the reaction and, particularly, on the initial formation of the 1,3-zwitterionic species through C-N bond cleavage, which has been found to be the rate-determining step. Compared to N-sulfonylaziridines, N-sulfamoylaziridines have proved to be more synthetically useful synthons that afford crystalline polycyclic structures in good yields. A short sequence of catalytic C(sp3)-H amination-cyclization-[3 + 2] cycloaddition has then been successfully designed to afford the homologue 1-azaspiro[5.n]alkanes, thereby illustrating the higher versatility of sulfamates in these cycloadditions.

Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations

The 7-coordinate complex [Fe(qpy)(MeCN)2](ClO4) 2 (1, qpy = 2,2′:6′,2″:6″, 2′′′:6′′′,2′′′′- quinquepyridine) is a highly active nonheme iron catalyst for intra- and intermolecular amination of C(sp3)-H bonds. This complex effectively catalyzes the amination of limiting amounts of not only benzylic and allylic C(sp3)-H bonds of hydrocarbons but also the C(sp3)-H bonds of cyclic alkanes and cycloalkane/linear alkane moieties in sulfamate esters, such as those derived from menthane and steroids cholane and androstane, using PhI=NR or "PhI(OAc)2 + H2NR" [R = Ts (p-toluenesulfonyl), Ns (p-nitrobenzenesulfonyl)] as nitrogen source, with the amination products isolated in up to 93% yield. Iron imide/nitrene intermediates [Fe(qpy)(NR)(X)]n+ (CX, X = NR, solvent, or anion) are proposed in these amination reactions on the basis of experimental studies including ESI-MS analysis, crossover experiments, Hammett plots, and correlation with C-H bond dissociation energies and with support by DFT calculations. Species consistent with the formulations of [Fe(qpy)(NTs)2] 2+ (CNTs) and [Fe(qpy)(NTs)]2+ (C) were detected by high-resolution ESI-MS analysis of the reaction mixture of 1 with PhI=NTs (4 equiv). DFT calculations revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of 7-coordinate C NTs and ground state of C are 15.3 and 14.2 kcal/mol, respectively, in line with the observed high activity of 1 in catalyzing the C-H amination of alkanes under mild conditions.

Catalyst-free aziridination and unexpected homologation of aziridines from imines

Aziridination and unpredicted homologation reaction of N-sulfonylimines were achieved easily with a very simple, rapid and mild procedure through the use of diazomethane without the presence of any catalyst. The method represents an attractive alternative

Copper-nitrenoid formation and transfer in catalytic olefin aziridination utilizing chelating 2-pyridylsulfonyl moieties

(Chemical Equation Presented) We have developed an efficient protocol for copper-catalyzed olefin aziridination using 5-methyl-2-pyridinesulfonamide or 2-pyridinesulfonyl azide as the nitrenoid source. The presence of a 2-pyridyl group significantly facil

Imido transfer from bis(imido)ruthenium(VI) porphyrins to hydrocarbons: Effect of imido substituents, C-H bond dissociation energies, and Ru VI/V reduction potentials

[RuVI(TMP)(NSO2R)2] (SO2R = Ms, Ts, Bs, Cs, Ns; R = p-C6H4OMe, p-C6H 4Me, C6H5, p-C6H4-Cl, p-C6H4NO2, respectively) and [Ru VI(Por)(NTs)2] (Por = 2,6-Cl2TPP, F 20-TPP) were prepared by the reactions of [RuII(Por)(CO)] with Phl=NSO2R in CH2Cl2. These complexes exhibit reversible RuVI/V couple with E1/2 = -0.41 to -0.12 V vs Cp2Fe+/10 and undergo imido transfer reactions with styrenes, norbornene, cis-cyclooctene, indene, ethylbenzenes, cumene, 9,10-dihydroanthracene, xanthene, cyclohexene, toluene, and tetrahydrofuran to afford aziridines or amides in up to 85% yields. The second-order rate constants (k2) of the aziridination/amidation reactions at 298 K were determined to be (2.6 ± 0.1) × 10-5 to 14.4 ± 0.6 dm3 mol-1 s-1, which generally increase with increasing RuVI/V reduction potential of the imido complexes and decreasing C-H bond dissociation energy (BDE) of the hydrocarbons. A linear correlation was observed between log K (K is the k2 value divided by the number of reactive hydrogens) and BDE and between log k2 and E1/2(RuVI/V); the linearity in the former case supports a H-atom abstraction mechanism. The amidation by [RuVI(TMP)(NNs) 2] reverses the thermodynamic reactivity order cumene > ethylbenzene/toluene, with K(3° C-H)/K(2° C-H) = 0.2 and K(3° C-H)/K(1° C-H) = 0.8.

Notable coordination effects of 2-pyridinesulfonamides leading to efficient aziridination and selective aziridine ring opening

(Chemical Equation Presented) We have developed, on the basis of a chelation-strategy, an efficient copper-catalyzed aziridination protocol with the use of 5-methyl-2-pyridinesulfonamide and Phl(OAc)2. The reaction proceeds smoothly under mild conditions to give aziridines in moderate to good yields in the absence of external ligands or bases. The coordination-assisted approach offers the additional benefits that efficient deprotection of the N-substituent and selective aziridine ring-opening are effectively achieved.