93008-98-1

Upstream product

• 496-11-7 INDANE 
• 19618-96-3 N-(4-Methylphenylsulfonyl)-peroxycarbamidsaeure-tert.-butylester 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 41085-71-6 bromamine T 
• 4083-64-1 Tosyl isocyanate 
• 6351-10-6 1-Indanol 
• 70-55-3 toluene-4-sulfonamide 
• 34698-41-4 2,3-dihydro-1H-inden-1-amine 
• 98-59-9 p-toluenesulfonyl chloride 
• 1593-60-8 p-toluenesulfonylhydroxylamine 
• 24425-40-9 indan-5-amine 
• 7080-50-4 chloramine-T hydrate 
• 127-65-1 chloroamine-T 
• 21849-40-1 dibromamine-T 

Downstream Products

• 10277-74-4 (S)-1-Aminoindane 
• 10277-74-4 (R)-1-Aminoindane 

Relevant academic research and scientific papers

Direct Synthesis of α-Amino Nitriles from Sulfonamides via Base-Mediated C-H Cyanation

Herein, we disclose a transition-metal-free reaction system that enables α-cyanation of sulfonamides through C-H bond cleavage for the preparation of α-amino nitriles, including difficult-to-access all-alkyl α-tertiary scaffolds. More than 50 substrate examples prove a wide functional group tolerance. Additionally, its synthetic practicality is highlighted by gram-scalability and the late-stage modification of natural compounds. Mechanistic experiments suggest that this process involves in situ formation of an imine intermediate via base-promoted elimination of HF.

Site-Selective Electrochemical Benzylic C?H Amination

C?H/N-H cross-coupling is an ideal strategy to synthesize various amines but remains challenging owing to the requirement for sacrificial chemical oxidants and the difficulty in controlling the regio- and chemo-selectivity. Herein we report a site-selective electrochemical amination reaction that can convert benzylic C?H bonds into C-N linkages via H2 evolution without need for external oxidants or metal catalysts. The synthetic strategy involves anodic cleavage of benzylic C?H to form a carbocation intermediate, which is then trapped with an amine nucleophile leading to C?N bond formation. Key to the success is to include HFIP as a co-solvent to modulate the oxidation potentials of the alkylbenzene substrate and the aminated product to avoid overoxidation of the latter.

Halogen-Bond-Induced Consecutive Csp3-H Aminations via Hydrogen Atom Transfer Relay Strategy

The utilization of a halogen bond in a number of chemical fields is well-known. Surprisingly, the incorporation of this useful noncovalent interaction in chemical reaction engineering is rare. We disclose here an uncommon use of halogen bonding to induce intermolecular Csp3-H amination while enabling a hydrogen atom transfer relay strategy to access privileged pyrrolidine structures directly from alkanes. Mechanistic studies support the presence of multiple halogen bond interactions at distinct reaction stages.

A Metal–Organic Framework with Exceptional Activity for C?H Bond Amination

The development of catalysts capable of fast, robust C?H bond amination under mild conditions is an unrealized goal despite substantial progress in the field of C?H activation in recent years. A Mn-based metal–organic framework (CPF-5) is described that promotes the direct amination of C?H bonds with exceptional activity. CPF-5 is capable of functionalizing C?H bonds in an intermolecular fashion with unrivaled catalytic stability producing >105 turnovers.

Organocatalytic nitrenoid transfer: Metal-free selective intermolecular C(sp3)-H amination catalyzed by an iminium salt

This report details the first organocatalytic method for nitrenoid transfer and its application to intermolecular, site-selective C(sp3)-H amination. The method utilizes a trifluoromethyl iminium salt as the catalyst, iminoiodinanes as the nitrogen source, and substrate as the limiting reagent. Activated, benzylic, and aliphatic substrates can all be selectively functionalized in yields up to 87%. A mechanistic proposal for the observed reactivity supported by experimental evidence invokes the intermediacy of a diaziridinium salt or related organic nitrenoid, species that have not been previously explored for the purpose of C-H amination. Finally, examples of late-stage functionalization of complex molecules highlight the selectivity and potential utility of this catalytic method in synthesis.

Nondirected, cu-catalyzed sp3 C-H aminations with hydroxylamine-based amination reagents: Catalytic and mechanistic studies

This work demonstrates the use of hydroxylamine-based amination reagents RSO2NH-OAc for the nondirected, Cu-catalyzed amination of benzylic C-H bonds. The amination reagents can be prepared on a gram scale, are benchtop stable, and provide benzylic C-H amination products with up to 86% yield. Mechanistic studies of the established reactivity with toluene as substrate reveal a ligand-promoted, Cu-catalyzed mechanism proceeding through Ph-CH2(NTsOAc) as a major intermediate. Stoichiometric reactivity of Ph-CH2(NTsOAc) to produce Ph-CH2-NHTs suggests a two-cycle, radical pathway for C-H amination, in which the decomposition of the employed diimine ligands plays an important role.

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.

Iron-catalyzed efficient intermolecular amination of C(sp3)-H bonds with bromamine-T as nitrene source

[Fe(N4Py)(CH3CN)](ClO4)2 can efficiently catalyze intermolecular nitrene insertion of sp3 C-H bonds with bromamine-T as the nitrene source, forming the desired tosylprotected amines with NaBr as the by-product.

Superacid synthesized tertiary benzenesulfonamides and benzofuzed sultams act as selective hCA IX inhibitors: Toward understanding a new mode of inhibition by tertiary sulfonamides

A series of tertiary (fluorinated) benzenesulfonamides was synthesized in superacid HF-SbF5. To circumvent the problem of the in situ iminium ion formation, proved by low temperature NMR experiments, a tandem superacid catalysed cross-coupling

Transition-metal-free benzylic C-H bond intermolecular amination utilizing chloramine-T and I2

An intermolecular benzylic C-H bond amination utilizing the combination of chloramine-T and I2 without the aid of transition-metal catalysts has been developed. The reaction was found applicable to a variety of benzene-substituted alkanes, as w