4948-76-9

Upstream product

• 498-66-8 norborn-2-ene 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 498-66-8 norbornene 
• 127-65-1 chloroamine-T 
• 55962-05-5 4-methyl-N-[(E)-phenyl-λ³-iodanylidene]benzenesulfonamide 

Downstream Products

• 497-38-1 Norbornan-2-on 
• 211747-63-6 exo-N-bicyclo[2.2.1]heptan-2-yl-4-methylbenzenesulfonamide 

Relevant academic research and scientific papers

Microencapsulated Cu(acac)2: A recoverable and reusable polymer-supported copper catalyst for aziridination of olefins

Microencapsulated copper(II) acetylacetonate was prepared and used in the aziridination of alkenes employing [N-(p-tolylsulfonyl)imino]phenyliodinane (PhI=NTs) as the nitrogen source. Microencapsulated copper(II) acetylacetonate [MC-Cu(acac)2] catalyst was reused for several cycles with consistent activity.

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.

Control of the platinum(II) ligating properties of rigid 1,2-diamines: the case of trans-2,3-diaminonorbornane

Guided by a simple predictive model, a norbornane-based trans-1,2-diamine was identified as a potential bridging ligand for di-nuclear platinum complex formation; efficient synthesis and product characterization confirmed this hypothesis.

Aziridination of alkenes and amidation of alkanes by bis(tosylimido)ruthenium(VI) porphyrins. A mechanistic study

Bis(tosylimido)ruthenium(VI) porphyrins, [Ru(VI)(Por)(NTs)2] (Por = TPP, TTP, 4-C1-TPP, 4-MeOTPP, OEP), were prepared in 60-74% yields by treatment of [Ru(II)(Por)(CO)(MeOH)] with (N-(p-tolylsulfonyl)- imino)phenyliodinane (PhI=NTS) in dichloromethane. In dichloromethane containing pyrazole, they reacted with alkenes or alkanes to give tosylamidoruthenium(IV) porphyrins, [Ru(IV)(Por)(NHTs)(pz)], in about 75% yields. The reactions of [Ru(VI)(TPP)(NTs)2] and [Ru(VI)(OEP)(NTs)2] with styrene, para-substituted styrenes, norbornene, cyclooctene, and β- methylstyrene afforded the corresponding N-tosylaziridines in 66-85% yields. The aziridination of cis-stilbene and cis-β-methylstyrene by [Ru(VI)(Por)(NTs)2] is nonstereospecific with a partial loss of the alkene stereochemistry. Kinetic studies on the reactions between [Ru(VI)(TPP)(NTs)2] and 16 alkenes (cyclooctene, norbornene, 2,3-dimethyl-2- butene, styrene, para-substituted styrenes, α and β-methylstyrene, and α- and β-deuteriostyrene) gave the second-order rate constants (k2) ranging from (1.60 ± 0.06) x 10-3 to (90 ± 4) x 10-3 dm3 mo1-1 s-1 at 298 K. The slope of the linear plot of log k2 vs E(l/2) for eight representative alkenes was found to be -1.7 V-1. In the case of para-substituted styrenes, linear correlation between log k(R) (k(R) = relative rate) and σ+ gives a ρ+ value as small as -1.1. However, the effect of para substituents on k(R) can be best accounted for by considering both the polar and spin delocalization effect. Measurements on the secondary deuterium isotope effect revealed that only the β-carbon atom of styrene experienced a significant change in its hybridization in reaching the transition state. All these are consistent with rate-determining formation of a carboradical intermediate. The reactions of [Ru(VI)(TPP)(NTs)2] and [Ru(VI-) (OEP)(NTs)2] with adamantane, cyclohexene, ethylbenzene, and cumene resulted in tosylamidation of these hydrocarbons and afforded the corresponding amides in 52-88% yields. For cyclohexane and toluene, the tosylamidation products were formed in poor yields (ca. 10%). Kinetic studies on the reactions between [Ru(VI-) (TPP)(NTs)2] and nine hydrocarbons (cumene, ethylbenzene, cyclohexene, and para-substituted ethylbenzenes) gave the second-order rate constants (k2) in the range of (0.330 ± 0.008) x 10-3 to (16.5 ± 0.3) x 10-3 dm3 mol-1 s-1. These reactions exhibit a large primary deuterium isotope effect, with a k(H)/k(D) ratio of 11 for the tosylamidation of ethylbenzene. In the case of para-substituted ethylbenzenes, both electron-donating and -withdrawing substituents moderately promote the reaction. There is an excellent linear correlation between log k(R) and a related carboradical parameter. On the basis of these observations, a mechanism involving the rate-limiting formation of a carboradical intermediate is postulated.

Nitrogen atom transfer to alkenes utilizing Chloramine-T as a nitrogen source

Aziridination of alkenes proceeds successfully using Chloramine-T (N-chloro-N-sodio-p-toluenesulfonamide). When anhydrous Chloramine-T was added to an acetonitrile solution of alkenes in the presence of various CuCl catalysts and MS-5A, the corresponding

Cleavage of sulfonamides with phenyldimethylsilyllithium

The toluene-p-sulfonamides of secondary amines and indoles are cleaved by treatment with phenyldimethylsilyllithium to give the secondary amines. Aziridine toluene-p-sulfonamides, however, are opened by attack of the silyllithium reagent on carbon to give β-silylethyl sulfonamides. The aziridine toluene-p-sulfonamide 22 derived from norbornene is different in giving the 2-[dimethyl(phenyl)silyl]-4-methylbenzenesulfonamide 23 of exo-norbornylamine. The aziridine toluene-p-sulfonamides 26, 28 and 30, derived from methyl cinnamate, methyl acrylate and cinnamyl acetate, are also anomalous, giving 3-[N-(p-tolylsulfonyl)amino]-3-phenylpropionic acid 27, {3-[N-(p-tolylsulfonyl)amino]propionyl}-dimethyl(phenyl)silane 29 and trans-cinnamyl alcohol 31, respectively, each derived by opening of the aziridine ring followed by loss of the silyl group.

Synthesis, characterisation and reactivity of novel bis(tosyl)imidoruthenium(VI) porphyrin complexes; X-ray crystal structure of a tosylamidoruthenium(IV) porphyrin

Bis(tosyl)imidoruthenium(VI) porphyrin complexes are prepared and characterised by spectroscopic means; [RuVI-(tpp)(NTs)2] can undergo imido group transfer reactions with alkenes to afford aziridines, as well as C-H bond oxidation of

Development of the copper-catalyzed olefin aziridination reaction

Soluble Cu(I) and Cu(II) triflate and perchlorate salts are efficient catalysts for the aziridination of olefins employing (N-(p-tolylsulfonyl)imino)phenyliodinane, PhI=NTs, as the nitrene precursor. Electron-rich as well as electron-deficient olefins und

Copper-Catalyzed Aziridination of Olefins by (N-(p-Toluenesulfonyl)imino)phenyliodinane

The Cu(I)- or Cu(II)-catalyzed aziridination of both electron-rich and electron-deficient olefins employing (N-(p-toluenesulfonyl)imino)phenyliodinane, PhI=NTs, as the nitrene precursor, affords N-tosylaziridines in yields ranging between 55percent - 95pe