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Upstream product

• 1883-96-1 N-benzylidenepyridin-2-amine 
• 917-64-6 methyl magnesium iodide 
• 109-04-6 2-bromo-pyridine 
• 618-36-0 rac-methylbenzylamine 
• 504-29-0 2-aminopyridine 
• 98-85-1 1-Phenylethanol 
• 372-48-5 2-fluoropyridine 
• 3886-69-9 (R)-1-phenyl-ethyl-amine 
• 109-09-1 2-chloropyridine 
• 2627-86-3 (S)-1-phenyl-ethylamine 
• 100-41-4 ethylbenzene 
• 98-86-2 acetophenone 
• 1541-40-8 2,3-dihydrothiazolo<3,2-a>pyridinium bromide 

Relevant academic research and scientific papers

ZnBr2 Mediated C?N Bond Formation using Cinnamyl Alcohol and 2-Amino Pyridines

A simple method for C?N bond formation is disclosed by using cinnamyl alcohols and 2-amino pyridine derivatives in the presence of stoichiometric amount of zinc bromide. This reaction works with a wide range of substrates, and is compatible with primary, secondary, and homoallylic alcohols. To the best of our knowledge, this is the first report for C?N bond formation using cinnamyl alcohol and 2-amino pyridines using zinc bromide as a Lewis acid.

Copper-catalyzed direct amination of benzylic hydrocarbons and inactive aliphatic alkanes with arylamines

A new synthetic method toward direct C-N bond formation through saturated C-H amination of benzylic hydrocarbons and inactive aliphatic alkanes with primary aromatic amines under an inexpensive catalyst/oxidant (Cu/DTBP) system has been developed. Both aminopyridines and anilines could react smoothly with primary and secondary benzylic C-H substrates or cyclohexane to form the corresponding aromatic secondary amines in moderate to good yields. This protocol has the advantages of wide functional group tolerance and use of readily available raw materials.

Copper(II) anilides in sp3 C-H amination

We report a series of novel β-diketiminato copper(II) anilides [Cl2NN]Cu-NHAr that participate in C-H amination. Reaction of H 2NAr (Ar = 2,4,6-Cl3C6H2 (Ar Cl3), 3,5-(CF3)2C6H3 (ArF6), or 2-py) with the copper(II) t-butoxide complex [Cl 2NN]Cu-tOBu yields the corresponding copper(II) anilides [Cl2NN]Cu-NHAr. X-ray diffraction of these species reveal three different bonding modes for the anilido moiety: κ1-N in the trigonal [Cl2NN]Cu-NHArCl3 to dinuclear bridging in {[Cl2NN]Cu}2(μ-NHArF6)2 and κ2-N,N in the square planar [Cl2NN] Cu(κ2-NH-2-py). Magnetic data reveal a weak antiferromagnetic interaction through a π-stacking arrangement of [Cl2NN]Cu- NHArCl3; solution EPR data are consistent with monomeric species. Reaction of [Cl2NN]Cu-NHAr with hydrocarbons R-H (R-H = ethylbenzene and cyclohexane) reveals inefficient stoichiometric C-H amination with these copper(II) anilides. More rapid C-H amination takes place, however, when tBuOOtBu is used, which allows for HAA of R-H to occur from the tBuO? radical generated by reaction of [Cl 2NN]Cu and tBuOOtBu. The principal role of these copper(II) anilides [Cl2NN]Cu-NHAr is to capture the radical R? generated from HAA by tBuO? to give functionalized aniline R-NHAr, resulting in a novel amino variant of the Kharasch-Sosnovsky reaction.

Solvent- and catalyst-free direct reductive amination of aldehydes and ketones with Hantzsch ester: Synthesis of secondary and tertiary amines

A facile and rapid method for the parallel synthesis of a series of secondary and tertiary amines by the direct reductive amination of aldehydes and ketones with Hantzsch ester under solvent- and catalyst-free has been developed. The scope and limitation of this method are described.

A metal-free tandem demethylenation/C(sp2)-H cycloamination process of N -Benzyl-2-aminopyridines via C-C and C-N bond cleavage

A mild, metal-free synthesis of pyrido[1,2-a]benzimidazoles starting with N-benzyl-2-aminopyridines, which employs PhI(OPiv)2 as a stoichiometric oxidant, has been developed. The process is initiated by an unusual PhI(OPiv)2-mediated ipso SEAr reaction, followed by solvent-assisted C-C and C-N bond cleavage.

An efficient palladium-catalyzed N-alkylation of amines using primary and secondary alcohols

PdCl2 in the presence of dppe or Xantphos(t-Bu) as the ligand is found to be an efficient catalyst for the N-alkylation of various primary and cyclic secondary amines using primary alcohols at 90-130 C under neat conditions. Interestingly, good to excellent yields were achieved when more challenging secondary alcohols were used as alkylating agents at 130-150 C. The reaction could be easily scaled up, as demonstrated for a 10 mmol scale achieving yields up to 90% with a TON of 900.

S-benzyl isothiouronium chloride as a recoverable organocatalyst for the direct reductive amination of ketones with Hantzsch ester

The direct reductive amination of ketones using the Hantzsch ester in the presence of S-benzyl isothiouronium chloride as a recoverable organocatalyst is reported. A wide range of ketones as well as amines were found to give the expected products in moder

N-Alkylation of poor nucleophilic amines and derivatives with alcohols by a hydrogen autotransfer process catalyzed by copper(II) acetate: Scope and mechanistic considerations

Copper(II) acetate is a versatile, cheap and simple catalyst for the selective N-monoalkylation of amino derivatives with poor nucleophilic character, such as aromatic and heteroaromatic amines as well as carboxamides, phosphinamides, sulfonamides, and phosphazenes, using in all cases primary alcohols as initial source of the electrophiles, through a hydrogen autotransfer process. In the case of sulfonamides, the monoalkylation process followed by a naphthalene-catalyzed reductive deprotection gives primary amines, which is an indirect alternative to the direct monoalkylation of ammonia. A study of the reaction using deuterium labelled reagents was performed, indicating that the dehydrogenation and hydrogenation steps do not take placed on the same copper-atom coordination sphere, with the condensation step occurring out of the dehydrogenating catalytic species.

Highly reactive, general and long-lived catalysts for palladium-catalyzed amination of heteroaryl and aryl chlorides, bromides, and iodides: Scope and structure-activity relationships

We describe a systematic study of the scope and relationship between ligand structure and activity for a highly efficient and selective class of catalysts containing sterically hindered chelating alkylphosphines for the amination of heteroaryl and aryl chlorides, bromides, and iodides. In the presence of this catalyst, aryl and heteroaryl chlorides, bromides, and iodides react with many primary amines in high yields with part-per-million quantities of palladium precursor and ligand. Many reactions of primary amines with both heteroaryl and aryl chlorides, bromides, and iodides occur to completion with 0.0005-0.05 mol % catalyst. A comparison of the reactivity of this catalyst for the coupling of primary amines at these loadings is made with catalysts generated from hindered monophosphines and carbenes, and these data illustrate the benefits of chelation. Studies on structural variants of the most active catalyst indicate that a rigid backbone in the bidentate structure, strong electron donation, and severe hindrance all contribute to its high reactivity. Thus, these complexes constitute a fourth-generation catalyst for the amination of aryl halides, whose activity complements catalysts based on monophosphines and carbenes.

A mild, catalyst-free synthesis of 2-aminopyridines

Alkylation of 2-mercaptopyridine with 1,2-dibromoethane affords a cyclic dihydrothiazolopyridinium salt that can serve as a precursor of 2-aminopyridines. Its reaction with primary or secondary amines, either neat or in DMSO, under mild conditions gives the title compounds.