4334-27-4

Upstream product

• 26930-67-6 N-(pyrid-2-ylmethylene)-p-methoxyphenylamine 
• 586-98-1 2-Hydroxymethylpyridine 
• 104-94-9 4-methoxy-aniline 
• 55401-97-3 2-(Bromomethyl)pyridine 
• 3731-51-9 2-(Aminomethyl)pyridine 
• 459-60-9 1-fluoro-4-methoxybenzene 
• 26930-67-6 (E)-N-(4-methoxyphenyl)-1-(pyridin-2-yl)methanimine 
• 6959-47-3 2-chloromethylpyridine hydrochloride 
• 1121-60-4 pyridine-2-carbaldehyde 

Downstream Products

• 14990-93-3 N-(4-methoxyphenyl)-2-pyridinecarboxamide 
• 26930-67-6 N-(pyrid-2-ylmethylene)-p-methoxyphenylamine 

Relevant academic research and scientific papers

Nucleophilic aromatic substitution of unactivated fluoroarenes enabled by organic photoredox catalysis

Nucleophilic aromatic substitution (SNAr) is a classical reaction with well-known reactivity toward electron-poor fluoroarenes. However, electron-neutral and electron-rich fluoro(hetero)arenes are considerably underrepresented. Herein, we present a method for the nucleophilic defluorination of unactivated fluoroarenes enabled by cation radical-accelerated nucleophilic aromatic substitution. The use of organic photoredox catalysis renders this method operationally simple under mild conditions and is amenable to various nucleophile classes, including azoles, amines, and carboxylic acids. Select fluorinated heterocycles can be functionalized using this method. In addition, the late-stage functionalization of pharmaceuticals is also presented. Computational studies demonstrate that the site selectivity of the reaction is dictated by arene electronics.

Manganese-Catalyzed Transfer Hydrogenation of Aldimines

The reduction of imines to amines via transfer hydrogenation was achieved promoted by phosphine-free manganese(I) catalyst. Using isopropanol as reductant, in the presence of tBuOK (4 mol %) and manganese complex [Mn(CO)3Br(κ2N,N-PyCH2NH2)] (2 mol %), a large variety of aldimines (30 examples) were typically reduced in 3 hours at 80 °C with good to excellent yield.

Zinc (II), palladium (II) and cadmium (II) complexes containing 4-methoxy-N-(pyridin-2-ylmethylene) aniline derivatives: Synthesis, characterization and methyl methacrylate polymerization

A series of Zn (II), Pd (II) and Cd (II) complexes, [(L)nMX2]m (L = L-a–L-c; M = Zn, Pd; X = Cl; M = Cd; X = Br; n, m = 1 or 2), containing 4-methoxy-N-(pyridin-2-ylmethylene) aniline (L-a), 4-methoxy-N-(pyridin-2-ylmethyl) aniline (L-b) and 4-methoxy-N-methyl-N-(pyridin-2-ylmethyl) aniline (L-c) have been synthesized and characterized. The X-ray crystal structures of Pd (II) complexes [L1PdCl2] (L = L-b and L-c) revealed distorted square planar geometries obtained via coordinative interaction of the nitrogen atoms of pyridine and amine moieties and two chloro ligands. The geometry around Zn (II) center in [(L-a)ZnCl2] and [(L-c)ZnCl2] can be best described as distorted tetrahedral, whereas [(L-b)2ZnCl2] and [(L-b)2CdBr2] achieved 6-coordinated octahedral geometries around Zn and Cd centers through 2-equivalent ligands, respectively. In addition, a dimeric [(L-c)Cd(μ-Br)Br]2 complex exhibited typical 5-coordinated trigonal bipyramidal geometry around Cd center. The polymerization of methyl methacrylate in the presence of modified methylaluminoxane was evaluated by all the synthesized complexes at 60°C. Among these complexes, [(L-b)PdCl2] showed the highest catalytic activity [3.80 × 104 g poly (methyl methacrylate) (PMMA)/mol Pd hr?1], yielding high molecular weight (9.12 × 105 g mol?1) PMMA. Syndio-enriched PMMA (characterized using 1H-NMR spectroscopy) of about 0.68 was obtained with Tg in the range 120–128°C. Unlike imine and amine moieties, the introduction of N-methyl moiety has an adverse effect on the catalytic activity, but the syndiotacticity remained unaffected.

TBAB-Catalyzed Csp3–N Bond Formation by Coupling Pyridotriazoles with Anilines: A New Route to (2-Pyridyl)alkylamines

A new metal-free procedure allowing Csp3–N bond formation through coupling of pyridotriazoles and weakly nucleophilic anilines has been developed. This sustainable reaction shows high tolerance towards functional groups (ketones, free alcohols) leading to 2-picolylamine derivatives. The key to our success is the use of a catalytic amount of TBAB and water as a co-solvent leading to the formation of pyridylalkylamine derivatives. As this coupling tolerates the presence of Csp2–Br bond on both partners of the reaction, we performed a sequential one-pot reaction between functionalized triazolopyridines and anilines followed by a second coupling with N-tosylhydrazones leading to the formation of Csp3–N and Csp2–Csp2 bonds.

Improving C=N bond reductions with (Cyclopentadienone)iron complexes: Scope and limitations

Herein, we broaden the application scope of (cyclo-pentadienone)iron complexes 1 in C=N bond reduction. The catalytic scope of pre-catalyst 1b, which is more active than the “Kn?lker complex” (1a) and other members of its family, has been expanded to the catalytic transfer hydrogenation (CTH) of a wider range of aldimines and ketimines, either pre-isolated or generated in situ. The kinetics of 1b-promoted CTH of ketimine S1 were assessed, showing a pseudo-first order profile, with TOF = 6.07 h–1 at 50 % conversion. Moreover, the chiral complex 1c and its analog 1d were employed in the enantioselective reduction of ketimines and reductive amination of ketones, giving fair to good yields and moderate enantioselectivity.

Efficient Synthesis of Amines by Iron-Catalyzed C=N Transfer Hydrogenation and C=O Reductive Amination

Here we report the catalytic transfer hydrogenation (CTH) of non-activated imines promoted by a Fe-catalyst in the absence of Lewis acid co-catalysts. Use of the (cyclopentadienone)iron complex 1, which is much more active than the classical ‘Kn?lker complex’ 2, allowed to reduce a number of N-aryl and N-alkyl imines in very good yields using iPrOH as hydrogen source. The reaction proceeds with relatively low catalyst loading (0.5–2 mol%) and, remarkably, its scope includes also ketimines, whose reduction with a Fe-complex as the only catalyst has little precedents. Based on this methodology, we developed a one-pot CTH protocol for the reductive amination of aldehydes/ketones, which provides access to secondary amines in high yield without the need to isolate imine intermediates. (Figure presented.).

A simple method for the synthesis of 1,3-diaminopropan-2-ols derivatives and their ex vivo relaxant activity on isolated rat tracheal rings

Abstract: A mild and eco-friendly method has been developed for the synthesis of a series of 1,3-diaminopropan-2-ols 8a–n. The epoxide of epichlorohydrin undergoes ring-opening with amines using MgSO4 or mixed metal oxides catalysts under mild

Experimental and mechanistic insights into copper(ii)-dioxygen catalyzed oxidative: N -dealkylation of N -(2-pyridylmethyl)phenylamine and its derivatives

A di-(2-pyridylmethyl)phenylamine ((PyCH2)2NPh) supported Cu(ii)/O2 catalytic system was explored with the synthesis of pyridylmethyl-based compounds of carboxylate (PyCOOH), amide (PyC(O)NHPh), and imine (PyCHNPh) from the oxidative N-dealkylation of N-(2-pyridylmethyl)phenylamine (PyCH2NHPh) and its derivatives, by means of controlling the addition of a base and/or water to the reaction system under a dioxygen atmosphere at room temperature. Experimental studies showed that the imine and amide species could be precursors in succession in the way to the final oxidation state of carboxylates. A cyclic catalytic mechanism was proposed including the base triggered C-H bond activation of the 2-pyridylmethyl group (PyCH2-) and the intermolecular Cu-OOH α-hydrogen atom abstraction from the coordinated imine substrate (PyCHNPh).

A Highly Efficient Base-Metal Catalyst: Chemoselective Reduction of Imines to Amines Using An Abnormal-NHC-Fe(0) Complex

A base-metal, Fe(0)-catalyzed hydrosilylation of imines to obtain amines is reported here which outperforms its noble-metal congeners with the highest TON of 17000. The catalyst, (aNHC)Fe(CO)4, works under very mild conditions, with extremely low catalyst loading (down to 0.005 mol %), and exhibits excellent chemoselectivity. The facile nature of the imine reduction under mild conditions has been further demonstrated by reducing imines towards expensive commercial amines and biologically important N-alkylated sugars, which are difficult to achieve otherwise. A mechanistic pathway and the source of chemoselectivity for imine hydrosilylation have been proposed on the basis of the well-defined catalyst and isolable intermediates along the catalytic cycle.

Carbon dioxide promoted reductive amination of aldehydes in water mediated by iron powder and catalytic palladium on activated carbon

A mixture of iron powder and catalytic palladium on activated carbon has been developed for reductive amination of various aromatic aldehydes, including 2-pyridinecarboxaldehyde, in water under CO2 atmosphere. The reversible reaction of CO2 with water could form carbonic acid and hydrogen transfer from water to Pd(0) took place with the presence of iron powder, leading to formation of high-active Pd hydrides for the reductive amination process. On the other hand, the reaction system could be inherently neutralized by ready removal of CO2, thus resulting in facile post-processing.