63065-67-8

Usage

InChI:InChI=1/C13H13N/c1-11-7-8-13(14-10-11)9-12-5-3-2-4-6-12/h2-8,10H,9H2,1H3

Upstream product

• 16214-99-6 N-benzyl-3-methyl-pyridinium chloride 
• 3510-66-5 2-Bromo-5-methylpyridine 
• 100-39-0 benzyl bromide 
• 108-99-6 3-Methylpyridine 
• 62673-31-8 benzyl(bromo)zinc 
• 18368-64-4 2-chloro-5-methylpyridine 
• 6921-34-2 benzylmagnesium chloride 
• 1003-73-2 3-picoline-N-oxide 
• 103-54-8 cinnamyl acetate 
• 100-44-7 benzyl chloride 
• 80772-87-8 2-benzyl-5-methylpyridine 1-oxide 

Downstream Products

• 233607-76-6 2(2,4-dinitrobenzyl)-5-methyl pyridine 
• 1416848-95-7 2-(2-(5-methylpyridin-2-yl)-1,2-diphenylethyl)malononitrile 
• 127581-43-5 (5-methylpyridin-2-yl)(phenyl)methanone 
• 80772-87-8 2-benzyl-5-methylpyridine 1-oxide 

Relevant academic research and scientific papers

Acylation of 2-benzylpyridine N-oxides and subsequent in situ [3,3]-sigamatropic rearrangement reaction

An effective method for the acylation of 2-benzylpyridine N-oxides and their fast in situ [3,3]-sigmatropic rearrangement was reported. This transformation has a wide substrate scope under mild conditions, giving moderate to excellent yields. The application for the synthesis of chiral phenyl-2-pyridylmethanol products was briefly explored. Furthermore, an interesting example of tandem substitution and in situ [3,3]-sigamatropic rearrangement of 2-benzylpyridine N-oxide with benzenecarboximidoyl chloride was reported.

Photocatalyzed ortho-Alkylation of Pyridine N-Oxides through Alkene Cleavage

A photocatalyzed reaction of pyridine N-oxides with alkenes gives ortho-alkylated pyridines with cleavage of the carbon–carbon double bond. Benzyl and secondary alkyl groups are incorporated at the ortho position of pyridines in one pot.

A VERSATILE LIGAND FOR PALLADIUM-CATALYZED META-C-H FUNCTIONALIZATIONS

A class of mono-protected 3-amino-2- hydroxypyridine (MPAHP) ligands that enable the meta- C-H arylation of anilines, phenols, phenylacetic acids, and biologically relevant heterocyclic compounds using norbornene as a transient mediator is disclosed. The applicability of this meta-arylation methodology in the pharmaceutical industry is illustrated for heteroaryl substrates and heteroaryl iodide coupling partners, a feat made possible by using the MPAHP ligand. The enabling nature of MPAHP ligands to achieve other meta-C-H functionalization processes is also illustrated by the development of a meta-C-H amination reaction and a meta-C-H alkynylation reaction.

Base metal-catalyzed benzylic oxidation of (aryl)(heteroaryl)methanes with molecular oxygen

The methylene group of various substituted 2- and 4-benzylpyridines, benzyldiazines and benzyl(iso)quinolines was successfully oxidized to the corresponding benzylic ketones using a copper or iron catalyst and molecular oxygen as the stoichiometric oxidant. Application of the protocol in API synthesis is exemplified by the alternative synthesis of a precursor to the antimalarial drug Mefloquine. The oxidation method can also be used to prepare metabolites of APIs which is illustrated for the natural product papaverine. ICP-MS analysis of the purified reaction products revealed that the base metal impurity was well below the regulatory limit.

Ligand-Promoted Meta-C-H Arylation of Anilines, Phenols, and Heterocycles

Here we report the development of a versatile 3-acetylamino-2-hydroxypyridine class of ligands that promote meta-C-H arylation of anilines, heterocyclic aromatic amines, phenols, and 2-benzyl heterocycles using norbornene as a transient mediator. More than 120 examples are presented, demonstrating this ligand scaffold enables a wide substrate and coupling partner scope. Meta-C-H arylation with heterocyclic aryl iodides as coupling partners is also realized for the first time using this ligand. The utility for this transformation for drug discovery is showcased by allowing the meta-C-H arylation of a lenalidomide derivative. The first steps toward a silver-free protocol for this reaction are also demonstrated.

Synthesis of Ni(II) complexes with unsymmetric [O,N,O′]-pincer ligands and their use as precatalysts in carbon-carbon bond formations to access diarylmethanes

1-Acetyl-[1a,3,5-CF3,1-C(=O)CH3] and 1-benzoyl-5-hydroxypyrazolines [1b, 3,5-CF3, 1-C(=O)C 6H5] have been synthesized and reacted with Ni(OAc) 2·4H2O in the presence of PPh3 to form square planar nickel complexes, which revealed a O,N,O′-coordination. An additional coordination site on the nickel center is occupied by one triphenylphosphane ligand. After having investigated the properties of the complexes, catalytic experiments have been carried out to synthesize diarylmethanes. Applying the complexes in the nickel-catalyzed carbon-carbon cross coupling of aryl halides with benzylzinc bromide excellent yields and selectivities of the corresponding diarylmethane have been obtained. Moreover, various experiments have been performed to shed light on the underlying reaction mechanism.

Application of nickel complexes modified by tridentate O,N,O'-ligands as precatalysts in nickel-catalyzed C(sp2)-C(sp3) bond formations

1-Acetyl- [1a; 3,5-CF3, 1-C(=O)CH3] and 1-benzoyl-5-hydroxypyrazolines [1b; 3,5-CF3, 1-C(=O)C 6H5] have been synthesized and treated with Ni(OAc) 2·4H2O in the presence of an excess of base [NH3 or 4-(dimethylamino)pyridine (DMAP)] to form the nickel complexes 4a-c. These complexes have been characterized by various techniques, which indicate a tridentate coordination mode of the ligands. X-ray crystallography determined an O,N,O'-coordination of the ligands, in which the ligand is planar, the oxygen donors are trans to each other, and the nitrogen donor is in a cis position. The other coordination sites on the nickel centre are occupied by the added base molecules (NH3 or DMAP). The number of NH3 or DMAP ligands depends on the nature of the base; in the case of ammonia, one molecule is coordinated to the nickel centre to form a diamagnetic square-planar complex, whereas with DMAP, an octahedral paramagnetic complex with three additional DMAP ligands was observed. Initial catalytic experiments have been performed by applying the complexes in the nickel-catalyzed C(sp2)-C(sp3) cross-coupling of aryl halides with benzylzinc bromides or dialkylzinc reagents; excellent yields and selectivities have been achieved.

Site selective processes: A combined theoretical and experimental investigation of thermally activated tautomerization processes in 2(2,4-dinitrobenzyl) pyridine derivatives

The thermally activated NH→CH tautomerization process in crystals of 2(2,4-dinitrobenzyl) pyridine derivatives was investigated. The results indicate the absence of any trivial molecular structure-reactivity correlation, in contrast to what is found for similar systems in solutions. The absence of molecular structure-reactivity correlation in the crystalline state is attributed to the participation of neighboring molecules in the proton transfer process. A combined experimental and theoretical approach is presented and applied to the study of the tautomerization reaction in crystalline environments. (C) 2000 Elsevier Science Ltd.

Flash Vacuum Pyrolysis of Substituted Pyridine N-Oxides and Its Application to Syntheses of Heterocyclic Compounds

Flash vacuum pyrolysis of 2-picoline N-oxide gave 2-picoline, pyridine, 2-ethylpyridine, 2-vinylpyridine, 2-pyridylmethanol, bis(2-pyridyl)methane, 1,2-bis(2-pyridyl)ethane, and 1,2-bis(2-pyridyl)ethylene.These reactions are explained by intermediary participation of the 2-picolyl radical.Flash vacuum pyrolysis of methyl-substituted 2-benzylpyridine N-oxides led to methyl-substituted pyridoindoles or to benzoquinoline in moderate yields.