147127-10-4

Upstream product

• 766-90-5 cis-1-phenyl-1-propylene 
• 41085-71-6 bromamine T 
• 873-66-5 1-propenylbenzene 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 70-55-3 toluene-4-sulfonamide 
• 637-50-3 1-phenylpropene 
• 76152-15-3 N-iodo-N-potassio-p-toluenesulphonamide 
• 98-83-9 isopropenylbenzene 

Downstream Products

• 1421527-39-0 N-[1-phenyl-1-(phenylsulfonyl)propan-2-yl]-4-methylbenzenesulfonamide 
• 1421527-50-5 C₂₂H₂₃NO₄S₂ 
• 1421527-38-9 C₂₃H₂₅NO₄S₂ 
• 1421527-46-9 C₂₃H₂₅NO₄S₂ 
• 64274-26-6 4-methyl-N-(1-oxo-1-phenylpropan-2-yl)benzene sulfonamide 
• 3893-40-1 N-(2-oxo-1-phenyl-propyl)-4-methyl-benzenosulfonamide 

Relevant academic research and scientific papers

Is the Electrophilicity of the Metal Nitrene the Sole Predictor of Metal-Mediated Nitrene Transfer to Olefins? Secondary Contributing Factors as Revealed by a Library of High-Spin Co(II) Reagents

Recent research has highlighted the key role played by the electron affinity of the active metal-nitrene/imido oxidant as the driving force in nitrene additions to olefins to afford valuable aziridines. The present work showcases a library of Co(II) reage

Chiral bis(pyrazolyl)methane copper(I) complexes and their application in nitrene transfer reactions

In this study, chiral bis(pyrazolyl)methane copper(I) acetonitrile complexes were applied to generate two novel terminal copper tosyl nitrene complexes with the nitrene generating agent SPhINTs in dichloromethane at low temperatures. The syntheses of the chiral bis(pyrazolyl)methane ligands are based on pulegone and camphor, members of the natural chiral pool. The chiral copper(I) acetonitrile complexes were applied as catalysts in the copper nitrene mediated aziridination reaction of different styrene derivatives and the C-H amination of various substrates. The reactions afforded good yields, but low enantiomeric excess under mild conditions. The nitrene species have been characterized with UV/Vis and EPR spectroscopy and the products of the decay by ESI mass spectrometry.

A bromo-capped diruthenium(i,i) N-heterocyclic carbene compound for in situ bromine generation with NBS: Catalytic olefin aziridination reactions

A bromo-capped metal-metal bonded diruthenium(i,i) complex Ru2(CO)4(PIN)2Br2 (1) (PIN = 1-isopropyl-3-(5,7-dimethyl-1,8-naphthyrid-2-yl)imidazol-2-ylidene) generates bromine with N-bromosuccinimide (NBS) at room temperature. Cycloalkene and stilbene are readily brominated by stoichiometric reactions with 1 and NBS. An analysis of the dibrominated products suggests the formation of cyclic bromonium intermediates indicating in situ Br2 generation. Complex 2, an iodide analogue of 1, is also synthesized. The reaction of 2 with N-iodosuccinimide releases I2, which is confirmed by the starch-iodine test. The catalytic utility of 1 is examined for the bromination of phenol. Catalyst 1, in combination with NBS and base, exhibits regioselectivity towards monobrominated products. Furthermore, efficient olefin aziridination is demonstrated utilizing catalyst 1 in the presence of NBS, K2CO3 and TsNH2.

Copper-Catalyzed Aziridination with Redox-Active Ligands: Molecular Spin Catalysis

Small-molecule catalysts as mimics of biological systems illustrate the chemists’ attempts at emulating the tantalizing abilities displayed by nature's metalloenzymes. Among these innate behaviors, spin multistate reactivity is used by biological systems as it offers thermodynamic leverage towards challenging chemical reactivity but this concept is difficult to translate into the realm of synthetic organometallic catalysis. Here, we report a rare example of molecular spin catalysis involving multistate reactivity in a small-molecule biomimetic copper catalyst applied to aziridination. This behavior is supported by spin state flexibility enabled by the redox-active ligand.

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.

Polynuclear copper(I) complexes with chelating bis- and tris-N-heterocyclic carbene ligands: Catalytic activity in nitrene and carbene transfer reactions

Di- and trinuclear complexes of copper(I) bearing bis- or tris-N-heterocyclic carbene ligands have been prepared and evaluated as catalysts in nitrene transfer reactions from PhI=NTs to unsaturated and saturated substrates (olefin aziridination and C-H bond amidation) and carbene transfer reactions from diazo compounds to olefins. The complexes exhibited moderate-to-high catalytic activity in both processes. The tosylamidation of C-H bonds, previously unreported with a NHC-containing copper catalyst, was promoted by the dinuclear complexes. Polynuclear oligo-NHC-copper complexes catalyse the transfer of carbene or nitrene fragments to unsaturated and saturated substrates. The first example of the tosylamidation of C-H bonds with a catalyst containing the NHCCu core is described. Copyright

The mechanism of the (bispidine)copper(ii)-catalyzed aziridination of styrene: A combined experimental and theoretical study

Experimental and DFT-based computational results on the aziridination mechanism and the catalytic activity of (bispidine)copper(I) and -copper(II) complexes are reported and discussed (bispidine = tetra- or pentadentate 3,7-diazabicyclo[3.1.1]-nonane derivative with two or three aromatic N donors in addition to the two tertiary amines). There is a correlation between the redox potential of the copper(II/I) couple and the activity of the catalyst. The most active catalyst studied, which has the most positive redox potential among all (bispidine)-copper(II) complexes, performs 180 turnovers in 30 min. A detailed hybrid density functional theory (DFT) study provides insight into the structure, spin state, and stability of reactive intermediates and transition states, the oxidation state of the copper center, and the denticity of the nitrene source. Among the possible pathways for the formation of the aziridine product, the stepwise formation of the two N-C bonds is shown to be preferred, which also follows from experimental results. Although the triplet state of the catalytically active copper nitrene is lowest in energy, the two possible spin states of the radical intermediate are practically degenerate, and there is a spin crossover at this stage because the triplet energy barrier to the singlet product is exceedingly high.

Catalytic aziridinations with copper(II) salen complexes

Three copper(II) complexes coordinated with salen ligands are synthesized, characterized, and examined for catalytic nitrene transfer reactions with a set of olefins. All three copper(II) complexes exhibit catalytic reactivity for the aziridination of styrene with PhI=NTs. Complex 3 is the most efficient catalyst for activated olefins (up to 94% yield). This complex is additionally characterized by X-ray crystallography, showing a highly distorted octahedral ligand surrounding the Cu atom having included in its coordination sphere an acetate ligand. The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2005.

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

Aziridination of alkenes using N-iodo-N-potassio-p-toluenesulphonamide as a nitrene precursor

N-Iodo-N-potassio-p-toluenesulphonamide was found to be a convenient nitrene precursor for the aziridination of alkenes in the presence of copper catalysts.