175222-95-4

Upstream product

• 149552-43-2 [N-(nosyl)imino]phenyliodinane 
• 110-83-8 cyclohexene 
• 22613-33-8 2-cyclohexenylamine hydrochloride 
• 98-74-8 4-Nitrobenzenesulfonyl chloride 
• 6325-93-5 p-nitrobenzenesulfonamide 
• 1521-51-3 rac-3-bromocyclohexene 
• 1165952-91-9 cyclohexa-1,3-diene 

Relevant academic research and scientific papers

Silver Salt-Mediated Allylation Reactions Using Allyl Bromides

A facile, efficient, and chemoselective synthesis of allylic amides has been developed. Allyl bromides were used as the precursors activated by silver triflate. A Ritter-type reaction readily proceeded to give various allyl amides under mild conditions. The reaction protocol was also applicable to different nucleophilic partners to give a wide range of allyl-substituted products in the absence of a base.

Iodine-catalyzed aminosulfonation of hydrocarbons by imidoiodinanes. a synthetic and mechanistic investigation

The amino-functionalization of a range of benzylic and some aliphatic saturated and unsaturated hydrocarbons by reaction with imido-iodinanes (PhI=NSO2Ar) is catalyzed by I2 under operationally simple and mild conditions. The first examples of 1,2-functionalization of unactivated C-H bonds using imido-iodinanes as aminating agents are reported. Mechanistic investigations, including Hammett analysis, kinetic isotope effects, a cyclopropane clock experiment, and stereoselectivity tests, are indicative of a stepwise pathway in C-N bond formation. Investigation into the nature of the active aminating species has led to the isolation of a novel aminating agent formulated as (ArSO2N)xIy (x = 1, y = 2; or x = 3, y = 4).

Zirconium-catalyzed intermolecular hydroamination of unactivated olefins

Highly efficient hydroamination reactions of sulfonamides, carboxamides, and carbamates with unactivated olefins catalyzed by simple and inexpensive zirconium salts under mild reaction conditions were presented for the practical preparation of various amines. These processes gave good to excellent yields of the addition products in Markovnikov addition fashion. Georg Thieme Verlag Stuttgart.

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.

cis- and trans-Stereoselective Epoxidation of N-Protected 2-Cyclohexen-1-ylamines

(Equation Presented) The first systematic study of the cis and trans stereoselectivity in the m-CPBA epoxidation of N-protected cyclic allylic amines has been completed. Mono-N-protected systems gave epoxides with cis stereochemistry (amides are better ci

Rhodium(II)-Catalyzed CH Insertions with imino>phenyl-λ3-iodane

The catalyzed decomposition of imino>phenyl-λ3-iodane (NsN=IPh) resulted in formal insertions into CH bonds, activated by phenyl or vinyl groups, or by O-substituents.Scope and limitations of the reaction were investigated.Yields of up to 84percent were achieved in the most favorable cases.Yields were enhanced by electron-releasing substituents and decreased by steric hindrance.Aziridination competed with allylic insertion with olefinic substrates.The insertion reaction proceeded with retention of configuration.With chiral RhII catalysts, a modest asymmetric induction was observed.A mechanism involving direct insertion by a Rh-complexed nitrene into the CH bond is proposed.

Rhodium(II)-catalyzed aziridinations and ch insertions with [N-(p-nitrobenzenesulfonyl)imino]phenyliodinane

The [Rh2(OAc)4]-catalyzed decomposition of NsN=IPh {[N-(p-nitrobenzenesulfonyl)imino]phenyliodinane} in the presence of olefins affords aziridines in yields of up to 85%. The aziridination of cis-hex-2-ene and cis-β-methylstyrene is stereospecific, but, cis-stilbene affords a 3:1 mixture of cis- and trans-aziridines in low yield. With chiral Rh(II) catalysts, optically active aziridines are formed having enantiomeric excesses of up to 73%. The NsN-IPh-[Rh2(OAc)4] system is also efficient for the allylic amination of olefins and for insertion into CH bonds, activated by phenyl or oxygen substituents.

A method for rhodium(II)-catalyzed aziridination of olefins

The [Rh2(OAc)4] catalyzed decomposition of (N-(p-nitrobenzenesulfonyl)imino)phenyliodinane (PhI=NNs) in the presence of olefins affords aziridines in yields of 18-85%. The aziridination of cis-β-methylstyrene (1h) and cis-hex-2-ene (