68162-86-7

Upstream product

• 618-36-0 rac-methylbenzylamine 
• 98-74-8 4-Nitrobenzenesulfonyl chloride 
• 100-41-4 ethylbenzene 
• 149552-43-2 [N-(nosyl)imino]phenyliodinane 
• 100-42-5 styrene 
• 6325-93-5 p-nitrobenzenesulfonamide 
• 73901-01-6 p-nitrobenzenesulfonyl azide 

Downstream Products

• 79867-70-2 (R/S)-4-amino-N-(1-phenylethyl)benzenesulfonamide 
• 87718-07-8 N-(2,3-epoxypropyl)-N-(α-methylbenzyl)-4-aminobenzenesulfonamide 
• 87689-78-9 N-(2,3-epoxypropyl)-N-(α-methylbenzyl)-4-nitrobenzenesulfonamide 

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.

Nitrene Insertion into Aromatic and Benzylic C?H Bonds Catalyzed by Copper Complexes of Fluorinated Bis- and Tris(pyrazolyl)borates

Fluorinated bis- and tris(pyrazolyl)boratocopper complexes catalyze the nitrene insertion to C?H bonds of aromatic hydrocarbons efficiently producing amination products in good to excellent yields at room temperature. Imidoiodanes, PhI=NTs (Ts=p-toluenesulfonyl) and PhI=NNs (Ns=p-nitrophenylsulfonyl) serve as the nitrene source. The bis(pyrazolyl)borate catalyst [H2B(3,5-(CF3)2Pz)2]Cu(NCMe) with PhI=NNs produced the arene C?H functionalized product of mesitylene in 87 % yield with only trace amounts of benzylic C?H insertion. The use of [H2B(3,5-(CF3)2-4-(NO2)Pz)2]Cu(NCMe) that has an even weakly donating pyrazolate generated the arene C?H insertion product exclusively. The tris(pyrazolyl)borate complex [HB(3,5-(CF3)2Pz)3]Cu(NCMe), in contrast, generated the benzylic amination product from mesitylene and PhI=NNs in 82 % yield with only very minor amounts of arene C?H functionalization. DFT calculations suggest that Cu-nitrene moiety generated from [HB(3,5-(CF3)2Pz)3]Cu(NCMe) and PhI=NNs activates the benzylic C?H bond of mesitylene via a hydrogen atom abstraction (HAA) followed by a radical rebound (RR) pathway, whereas the functionalization of sp2 C?H bonds of mesitylene by [H2B(3,5-(CF3)2Pz)2]Cu(NNs) ensues possibly via a nitrene addition to the arene core.

Kinetic Resolution of Benzylamines via Palladium(II)-Catalyzed C-H Cross-Coupling

A Pd(II)-catalyzed enantioselective C-H cross-coupling of benzylamines via kinetic resolution has been achieved using chiral mono-N-protected α-amino-O-methylhydroxamic acid (MPAHA) ligands. Both chiral benzylamines and ortho-arylated benzylamines are obtained in high enantiomeric purity. The use of a readily removable nosyl (Ns) protected amino group as the directing group is a crucial practical advantage. Moreover, the ortho-arylated benzylamine products could be further transformed into chiral 6-substituted 5,6-dihydrophenanthridines as important structural motifs in natural products and bioactive molecules.

Glycoporphyrin Catalysts for Efficient C-H Bond Aminations by Organic Azides

We report herein the synthesis of new glycoporphyrin ligands which bear a glucopyranoside derivative on each meso-aryl moiety of the porphyrin skeleton. The saccharide unit is directly conjugated to the porphyrin or a triazole spacer is placed between the carbohydrate and porphyrin ring. The obtained glycoporphyrin ligands were employed to synthesize cobalt(II), ruthenium(II), and iron(III) complexes which were tested as catalysts of C-H bond aminations by organic azides. Two of the synthesized complexes were very efficient in promoting catalytic reactions, and the results achieved indicated that ruthenium and iron complexes show an interesting complementary catalytic activity in several amination reactions. The eco-friendly iron catalyst displayed very good chemical stability in catalyzing the amination reaction for three consecutive runs without losing catalytic activity. (Chemical Equation Presented).

Nonheme iron-mediated amination of C(sp3)-H bonds. Quinquepyridine-supported iron-imide/nitrene intermediates by experimental studies and DFT calculations

The 7-coordinate complex [Fe(qpy)(MeCN)2](ClO4) 2 (1, qpy = 2,2′:6′,2″:6″, 2′′′:6′′′,2′′′′- quinquepyridine) is a highly active nonheme iron catalyst for intra- and intermolecular amination of C(sp3)-H bonds. This complex effectively catalyzes the amination of limiting amounts of not only benzylic and allylic C(sp3)-H bonds of hydrocarbons but also the C(sp3)-H bonds of cyclic alkanes and cycloalkane/linear alkane moieties in sulfamate esters, such as those derived from menthane and steroids cholane and androstane, using PhI=NR or "PhI(OAc)2 + H2NR" [R = Ts (p-toluenesulfonyl), Ns (p-nitrobenzenesulfonyl)] as nitrogen source, with the amination products isolated in up to 93% yield. Iron imide/nitrene intermediates [Fe(qpy)(NR)(X)]n+ (CX, X = NR, solvent, or anion) are proposed in these amination reactions on the basis of experimental studies including ESI-MS analysis, crossover experiments, Hammett plots, and correlation with C-H bond dissociation energies and with support by DFT calculations. Species consistent with the formulations of [Fe(qpy)(NTs)2] 2+ (CNTs) and [Fe(qpy)(NTs)]2+ (C) were detected by high-resolution ESI-MS analysis of the reaction mixture of 1 with PhI=NTs (4 equiv). DFT calculations revealed that the reaction barriers for H-atom abstraction of cyclohexane by the ground state of 7-coordinate C NTs and ground state of C are 15.3 and 14.2 kcal/mol, respectively, in line with the observed high activity of 1 in catalyzing the C-H amination of alkanes under mild conditions.

Design, synthesis and in vitro antitumor evaluation of novel diaryl urea derivatives bearing sulfonamide moiety

A novel series of diaryl urea derivatives bearing sulfonamide moiety have been designed and synthesized. Their in vitro antitumor effect against human cancer cell lines MX-1, A375, HepG2, Ketr3 and HT-29 was screened and evaluated by the standard MTT assa

Au(iii)-catalyzed intermolecular amidation of benzylic C-H bonds

Au(iii)-catalyzed intermolecular amidations of benzylic C-H bonds with sulfonamides and carboxamides are described. The protocol with the Au-bipy complex/N-bromosuccinimide system provides practical applications for synthesis of various amides via C-H activations. The reaction proceeds with high efficiency to give the corresponding amines, which are extremely useful synthetic intermediates.

Discovery of salermide-related sirtuin inhibitors: Binding mode studies and antiproliferative effects in cancer cells including cancer stem cells

Chemical changes performed on 1a (sirtinol) led to a series of SIRT1/2 inhibitors, in some cases more potent than 1a mainly against SIRT1. Tested in human leukemia U937 cells, the benzamide and anilide derivatives 1b, 1c, 2b, and 2c as well as the 4-(2-phenylpropyl)thioanalogue 4c showed huge apoptosis induction, while some sulfinyl and sulfonyl derivatives (5b, 5c, and 6a-c) were highly efficient in granulocytic differentiation. When assayed in human leukemia MOLT4 as well as in human breast MDA-MB-231 and colon RKO cancer cell lines, the anilide 2b (salermide) and the phenylpropylthio analogue 4b emerged as the most potent antiproliferative agents. Tested on colorectal carcinoma and glioblastoma multiforme cancer stem cells (CSCs) from patients, 2b was particularly potent against colorectal carcinoma CSCs, while 4b, 6a, and the SIRT2-selective inhibitor AGK-2 showed the highest effect against glioblastoma multiforme CSCs. Such compounds will be further explored for their broad-spectrum anticancer properties.

Acyl derivatives of p-aminosulfonamides and dapsone as new inhibitors of the arginine methyltransferase hPRMT1

Arginine methylation is an epigenetic modification that receives increasing interest as it plays an important role in several diseases. This is especially true for hormone-dependent cancer, seeing that histone methylation by arginine methyltransferase I (PRMT1) is involved in the activation of sexual hormone receptors. Therefore, PRMT inhibitors are potential drugs and interesting tools for cell biology. A dapsone derivative called allantodapsone previously identified by our group served as a lead structure for inhibitor synthesis. Acylated derivatives of p-aminobenzenesulfonamides and the antilepra drug dapsone were identified as new inhibitors of PRMT1 by in vitro testing. The bis-chloroacetyl amide of dapsone selectively inhibited human PRMT1 in the low micromolar region and was selective for PRMT1 as compared to the arginine methyltransferase CARM1 and the lysine methyltransferase Set7/9. It showed anticancer activity on MCF7a and LNCaP cells and blocked androgen dependent transcription specifically in a reporter gene system. Likewise, a transcriptional block was also demonstrated in LNCaP cells using quantitative RT-PCR on the mRNA of androgen dependent genes.

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).