668994-46-5

Upstream product

• 908094-04-2 phenyldiazomethane 
• 51608-60-7 phenyl N-tosyl imine 
• 645-49-8 cis-stilben 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 51608-60-7 N-(benzylidene)-p-methylbenzenesulfonamide 
• 100-39-0 benzyl bromide 
• 55962-05-5 4-methyl-N-[(E)-phenyl-λ³-iodanylidene]benzenesulfonamide 
• 41085-71-6 bromamine T 
• 588-59-0 stilbene 
• 70-55-3 toluene-4-sulfonamide 
• 103-30-0 (E)-1,2-diphenyl-ethene 
• 127-65-1 chloroamine-T 
• 27992-27-4 sodium 2-benzylidene-1-tosylhydrazin-1-ide 
• 473-34-7 N,N-dichloro-p-toluenesulfonamide 

Downstream Products

• 124293-69-2 (2S,3S)-2,3-Diphenyl-1-(toluene-4-sulfonyl)-azetidine 

Relevant academic research and scientific papers

A versatile tripodal Cu(I) reagent for C-N bond construction via nitrene-transfer chemistry: Catalytic perspectives and mechanistic insights on C-H aminations/amidinations and olefin aziridinations

A CuI catalyst (1), supported by a framework of strongly basic guanidinato moieties, mediates nitrene-transfer from PhI=NR sources to a wide variety of aliphatic hydrocarbons (C-H amination or amidination in the presence of nitriles) and olefins (aziridination). Product profiles are consistent with a stepwise rather than concerted C-N bond formation. Mechanistic investigations with the aid of Hammett plots, kinetic isotope effects, labeled stereochemical probes, and radical traps and clocks allow us to conclude that carboradical intermediates play a major role and are generated by hydrogen-atom abstraction from substrate C-H bonds or initial nitrene-addition to one of the olefinic carbons. Subsequent processes include solvent-caged radical recombination to afford the major amination and aziridination products but also one-electron oxidation of diffusively free carboradicals to generate amidination products due to carbocation participation. Analyses of metal- and ligand-centered events by variable temperature electrospray mass spectrometry, cyclic voltammetry, and electron paramagnetic resonance spectroscopy, coupled with computational studies, indicate that an active, but still elusive, copper-nitrene (S = 1) intermediate initially abstracts a hydrogen atom from, or adds nitrene to, C-H and C=C bonds, respectively, followed by a spin flip and radical rebound to afford intra- and intermolecular C-N containing products.

Metal-free aziridination of styrene derivatives with iminoiodinane catalyzed by a combination of iodine and ammonium iodide

The metal-free catalytic aziridination of styrene derivatives with N-tosyliminophenyliodinane (PhI=NTs) in the presence of a combination of I 2 and tetrabutylammonium iodide (TBAI) is reported. In situ generated TBAI3 from I2/s

Half-sandwich scorpionates as nitrene transfer catalysts

Scorpionate complexes of the middle to late 3d transition metals [(L)M(NCMe)3](BF4)n (M = Mn, Fe, Co, Ni: 1 M, L = tris(3,5-dimethylpyrazol-1-yl)methane, TpmMe,Me, n = 2; 2M, L = tris(3-phenylpyrazol-1-yl)methane, TpmPh, n = 2; 3M except 3Mn, L = hydrotris(3,5-dimethylpyrazol-1-yl) borate, [TpMe,Me]-, n = 1; 4M, L = hydrotris(3-phenyl-5-methylpyrazol-1-yl)borate, [TpPh,Me] -, n = 1) were examined as catalysts for styrene aziridination and THF amination using phenyl-N-tosyliodinane as a nitrene donor. [(Tpm Me,Me)Fe(NCMe)3](BF4)2 (1 Fe) was identified as the most active catalyst, giving nearly quantitative nitrene transfer yields at 5 mol % loadings. The reactivity of 1Fe with a wider range of organic substrates was also explored, and a striking observation was strong selectivity for aromatic rather than benzylic amination for alkylaromatic substrates.

Nickel-catalyzed negishi alkylations of styrenyl aziridines

A nickel-catalyzed cross-coupling reaction between N-sulfonyl aziridines and organozinc reagents is reported. The catalytic system comprises an inexpensive and air-stable Ni(II) source and dimethyl fumarate as ligand. Regioselective synthesis of β-substituted amines is possible under mild and functional-group-tolerant conditions. The stereoselectivity of the reaction is consistent with a stereoconvergent mechanism wherein the sulfonamide directs C-C bond formation.

Copper(ii) complexes incorporating poly/perfluorinated alkoxyaluminate-type weakly coordinating anions: Syntheses, characterization and catalytic application in stereoselective olefin aziridination

The synthesis and characterization of a series of cationic copper(ii) complexes of the type [Cu(NCR)6][Al(OC(CF3) 2R′)4]2 (R = CH3, Ph; R′ = CF3, Ph, PhCH3), incorpora

Sulfur ylide promoted synthesis of N-protected aziridines: A combined experimental and computational approach

A range of N-protected aziridines [N-Tosyl (N-Ts), N-2- trimethylsilylethanesulfonamide (N-SES), N-tertbutoxycarbonylamido (N-Boc), and N-o-nitrobenzenesulfonamide (oNs)] were prepared in moderate to good yield and with high enantiomeric excess of both isomers starting from N-protected imines, using a sulfonium salt derived from Eliel's oxathiane. The diastereoselectivities of the reactions are influenced by the imine N-protecting group, the imine substituent, and the sulfide structure. An unusual cis selectivity was observed in the formation of N-tosyl-2-phenyl-3-tert- butylaziridine and N-o-trimethylsilylethanesulfonamide-2-phenyl-3-tert- butylaziridine, which was explained by using computational models. The analysis suggests that betaine formation in the case of N-tosyl-tert-butylaldimine aziridination using oxathiane benzyl sulfonium ylide 1′ is reversible and that the selectivity is determined at the rotation step, which is unusual for semistabilized ylide aziridination. We have shown herein that the steric bulk of an imine substituent, in combination with a sterically demanding sulfonium ylide, can also affect the reversibility of the reaction. This is the first example of this sort involving aziridinations using semistabilized ylides.

Highly enantioselective aziridination of N-protected imines: Comparison of the phosphazene EtP2 and sodium hydride as bases

Asymmetric synthesis of 2,3-disubstituted N-Boc, N-SES, and N-Ts aziridines starting from N-protected imines, using sulfonium salt derived from Eliel's oxathiane, is reported. Sodium hydride was successfully used as a substitute for the phosphazene base EtP2 without any loss of yield, enantioselectivity, or diastereoselectivity. Georg Thieme Verlag Stuttgart.

Syntheses of acetonitrile ligated copper complexes with perfluoroalkoxy aluminate as counter anion and their catalytic application for olefin aziridination

Acetonitrile ligated copper complexes with perfluoroalkoxy aluminate Al {OC (CF3)3}4- as weakly coordinating counter anion are successfully synthesized. Aziridination of various olefins with PhINTs catalyzed by

Cobalt-catalyzed efficient aziridination of alkenes

(Chemical Equation Presented) Cobalt porphyrins are capable of catalyzing the aziridination of alkenes with bromamine-T as the nitrene source. Among cobalt complexes of different porphyrins, Co(TDCIPP) is an effective catalyst that can aziridinate a wide

Two-Step Asymmetric Synthesis of Disubstituted N-Tosyl Aziridines Having 98-100% ee: Use of a Phosphazene Base

Unknown diaryl (1-3) and alkyl-phenyl (4, 5) N-tosyl aziridines have been successfully synthesized from pure (R,R,R,SS)-(-)-sulfonium salt derived from Eliel's oxathiane, tosylimines 11a-f, and using a phosphazene base (EtP2) to gene