66898-03-1

Upstream product

• 98-59-9 p-toluenesulfonyl chloride 
• 585-32-0 2-phenyl-2-propylamine 
• 98-82-8 Isopropylbenzene 
• 18522-92-4 sodium p-toluenesulfonamide 
• 55962-05-5 [N-(p-tolylsulfonyl)imino]phenyliodinane 
• 70-55-3 toluene-4-sulfonamide 
• 98-83-9 isopropenylbenzene 
• 127-65-1 chloroamine-T 
• 4019-54-9 isopropylbenzene-d1 
• 21849-40-1 dibromamine-T 
• 7774-60-9 α,α-dimethylbenzyl 2-methylpropanoate 
• 7080-50-4 chloramine-T hydrate 
• 41085-71-6 bromamine T 
• 100-41-4 ethylbenzene 

Downstream Products

• 66897-71-0 N-Allyl-4-methyl-N-(1-methyl-1-phenyl-ethyl)-benzenesulfonamide 
• 936841-25-7 2-iodo-4-methyl-N-(2-phenylpropan-2-yl)benzenesulfonamide 
• 936841-47-3 4-methyl-2-phenyl-N-(2-phenylpropan-2-yl)benzenesulfonamide 

Relevant academic research and scientific papers

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.

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.

NEW COMPOUNDS INHIBITORS OF THE YAP/TAZ-TEAD INTERACTION AND THEIR USE IN THE TREATMENT OF MALIGNANT MESOTHELIOMA

The invention relates to compounds of formula (I) wherein R1, R2, R3, R4, R5 and R6 are as defined in the description. The compounds of formula (I) are inhibitors of the YAP/TAZ-TEAD intera

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.

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.

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

NAlkylation of tosylamides using esters as primary and tertiary alkyl sources: Mediated by hydrosilanes activated by a ruthenium catalyst

Select your group: Either a primary or tertiary alkyl group can be selectively introduced onto the nitrogen atom of tosylamides in a ruthenium-catalyzed reaction employing hydrosilanes through a judicious choice in the esters that serve as the alkyl source (see scheme; Ts= 4-toluenesulfonyl). These N-alkylation reactions are useful for construction of naturally occurring azacyclic skeletons. Copyright

A highly efficient catalyst-free protocol for C-H bond activation: Sulfamidation of alkyl aromatics and aldehydes

A catalyst-free protocol has been developed for amidation of alkyl aromatics and aldehydes using TsNBr2via a nitrene transfer process in the presence of a base in excellent yield within a short time. The reaction was found to be selective for secondary and tertiary benzylic C-H bonds and C-H bonds of aldehydic groups.

On the mechanism of ligand-assisted, copper-catalyzed benzylic amination by chloramine-T

The mechanism of hydrocarbon amination by chloramine-T derivatives catalyzed by (diimine)copper complexes has been investigated. The initial synthetic study of the reactions revealed ligand-accelerated catalysis, significant sensitivity to the electronic character of the substrates, and low to moderate enantioselectivities with homochiral ligands. Various mechanistic probes, both experimental and computational, have been focused on the C-H insertion process. A kinetic isotope effect of 4.6 was found in the amination of α-D(H)-cumenes catalyzed by [(diimine)Cu(solv)]Z. Amination of the isomeric substrates cis-and trans-4-tert-butyl-1-phenylcyclohexanes with 4-Me-C6H4SO2NNaCl (chloramine-T) or 4-NO 2-C6H4SO2NNaCl (chloramine-N) catalyzed by [(diimine)Cu(CH3CN)]PF6 produced in all cases an approximately 1:1 mixture of the corresponding cis-and trans-4-tert-butyl-1- phenyl-1-sulfonaminocyclohexanes. Amination of the radical-clock substrate 1-phenyl-2-benzylcyclopropane with chloramine-T/(diimine)Cu(CH 3CN)]PF6 gave a mixture of ring-opened and cyclopropylmethylamino derivatives. Together, these results are most consistent with a stepwise insertion of an N-Ts(Ns) unit into the C-H bond, via carbon radicals, and a secondary contribution from a concerted insertion pathway. B3LYP and CASSCF computations suggest that the C-H insertion step involves the reaction of the hydrocarbon with a Cu-imido (nitrene) complex, [(diimine)Cu=NSO2R]+. The ground-state triplet of the Cu-imido complex is calculated to be 3-13 kcal/mol more stable that the singlet complex, depending on the method and basis sets employed. The reaction of each complex with toluene is modeled to find that the C-H insertion transition state for the triplet (ΔG? = 8.2 kcal/mol) is lower in energy than the singlet. The former reacts by a stepwise H-atom abstraction, while the latter reacts by a concerted C-H insertion. These results and kinetic isotope effect calculations for the singlet (2.9) and triplet (4.8) pathways, respectively, agree with the experimental observations (4.6) and point to a major role for the triplet complex in the stepwise, nonstereoselective insertion pathway.