Experimental and mechanistic insights into copper(<scp>ii</scp>)–dioxygen catalyzed oxidative N-dealkylation of N-(2-pyridylmethyl)phenylamine and its derivatives

Liu, Haixiong; Zhang, Xiaofeng; Zhang, Zilong; Huang, Deguang

doi:10.1039/c7ob02192e

Cited by 10 publications

(11 citation statements)

References 35 publications

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“…For PY-COF, the imine (7′) and the pyridine (10′) nitrogen appear between −40 ppm and −78 ppm. The signal at −262 ppm in the 15 N ssNMR spectrum of PY-COF probably arises from oxidation of a fraction of the imine-linkages to amides in the COF (Supplementary Figs 9, 10, Supplementary Table 1) 43–47 . Interestingly, both PT- and PY-COFs show the presence of free amine functional groups (9 and 9′) at −323 ppm to −330 ppm (Fig.…”

Section: Resultsmentioning

confidence: 99%

Sub-stoichiometric 2D covalent organic frameworks from tri- and tetratopic linkers

Banerjee

Haase

Trenker³

et al. 2019

Nat Commun

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Covalent organic frameworks (COFs) are typically designed by breaking down the desired network into feasible building blocks - either simple and highly symmetric, or more convoluted and thus less symmetric. The linkers are chosen complementary to each other such that an extended, fully condensed network structure can form. We show not only an exception, but a design principle that allows breaking free of such design rules. We show that tri- and tetratopic linkers can be combined to form imine-linked [4 + 3] sub-stoichiometric 2D COFs featuring an unexpected bex net topology, and with periodic uncondensed amine functionalities which enhance CO 2 adsorption, can be derivatized in a subsequent reaction, and can also act as organocatalysts. We further extend this class of nets by including a ditopic linker to form [4 + 3 + 2] COFs. The results open up possibilities towards a new class of sub-valent COFs with unique structural, topological and compositional complexities for diverse applications.

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Section: Resultsmentioning

confidence: 99%

Sub-stoichiometric 2D covalent organic frameworks from tri- and tetratopic linkers

Banerjee

Haase

Trenker³

et al. 2019

Nat Commun

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“…Complex 1a Zn contains two independent molecules in the unit cell. Both independent molecules of 1a Zn are penta-coordinated, having distorted square pyramidal [ZnBr 2 N 3 ] geometry (τ 1 = 0.34 and τ 2 = 0.17, respectively), 23 where the ligand is coordinated meridionally [angle N1−Zn− N3 = 152.36 (10)°for Zn1 and 150.34 (10)°for Zn2, angles between pyridine planes are 12.19 (15)°and 10.88(15)°, respectively]. The remaining two coordination sites of the central zinc cation are occupied by bromide anions.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…In the crystal structure of 1b Zn , the PF 6 − anion was not incorporated, but it was a polymorph of 1a Zn , with a penta-coordinated zinc atom and ML stoichiometry. As opposed to 1a Zn , in 1b Zn the ligand is coordinated facially [angle N1−Zn−N3 = 109.56 (15)°, angle between pyridine planes = 79.1(2)°]. The [ZnBr 2 N 3 ] coordination polyhedron in 1b Zn is at the border between a trigonal bipyramid and square pyramid (τ = 0.50).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Structural Variety of Isopropyl-bis(2-picolyl)amine Complexes with Zinc(II) and Copper(II)

Juraj

Muratović

Perić

et al. 2020

Crystal Growth & Design

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A variety of structurally different complexes of the isopropyl-bis(2-picolyl)amine ( i Pr-bpa) ligand were prepared with ZnA2 and CuA2 salts (A = Br–, Br–/PF6 –, BF4 –/F–, ClO4 –). The choice of different counterion affected the stoichiometry, coordination number, geometry, and formation of geometrical isomers. Crystal structures of four Zn(II) complexes, namely, two monomers ( mer -[Zn( i Pr-bpa)Br 2 ] and fac -[Zn( i Pr-bpa)Br 2 ]), one F–-bridged dimer ([Zn 2 (μ-F) 2 ( i Pr-bpa) 2 ](BF 4 ) 2 ), and one ML 2 complex ([Zn( i Pr-bpa) 2 ](ClO 4 ) 2 ) were determined, and their solution structures were studied by NMR spectroscopy. For the ML 2 complex, relative stabilities of geometrical isomers were determined using density functional theory calculations. For Cu(II) complexes, five crystal structures were determined, namely, two monomers ([Cu( i Pr-bpa)Br 2 ] and [Cu( i Pr-bpa)(ClO 4 ) 2 (H 2 O)]), a Br–-bridged dimer ([Cu 2 (μ-Br)(Br) 2 ( i Pr-bpa) 2 ](PF 6 )), a F–-bridged coordination polymer ([Cu(μ-F)( i Pr-bpa)] n (BF 4 ) n × nCH 3 OH), and a cyclic, CO3 2–-bridged trimer ([Cu 3 (tri-μ-CO 3 )(ClO 4 ) 3 ( i Pr-bpa) 3 ](ClO 4 )). The different crystallographic structures of Cu(II) complexes are reflected in their different magnetic properties investigated by electron spin resonance spectroscopy and magnetic susceptibility measurements.

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“…The precursor complexes [Ru(Cl)(H)(CO)(PPh 3 ) 3 ] and ctc -[Ru(pap) 2 (EtOH) 2 ] and the ligands HL1 – HL4 − were prepared by following the literature procedures. Newly designed HL5 – HL7 were synthesized by following a procedure similar to that for HL4 .…”

Section: Methodsmentioning

confidence: 99%

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

et al. 2020

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Chemical noninnocence" of metal-coordinated 2-picolylamine (PA) derivatives has been introduced upon its reaction with the metal precursor [Ru II (Cl)-(H)(CO)(PPh 3 ) 3 ] under basic conditions. This in effect leads to the facile formation of metalated amide, imine, ring-cyclized pyrrole, and an N-dealkylated congener based on the fine-tuning of an amine nitrogen (N amine ) and a methylene center (C α ) at the PA backbone. It develops oxygenated L1′ in 1 and cyclized L4′ in 4 upon switching of the N amine substituent of PA from aryl to an electrophilic pent-3-en-2-one moiety. On the other hand, imposing the substituent at the C α position of PA modifies its reactivity profile, leading to a dehydrogenation (2/3) or N-dealkylation (6) process. The divergent reactivity profile of metalated PA is considered to proceed through a common dianionic intermediate. Further, a competitive scenario of C−H bond functionalization of coordinated PA versus the ligand-exchange process has been exemplified in the presence of external electrophile such as benzyl bromide or methylene iodide. Authentication of the product formation as well as elucidation of the reaction pathway has been addressed by their crystal structures and spectroscopic features in conjunction with the transition-state (TS) theory.

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

Cited by 10 publications

References 35 publications

Sub-stoichiometric 2D covalent organic frameworks from tri- and tetratopic linkers

Sub-stoichiometric 2D covalent organic frameworks from tri- and tetratopic linkers

Structural Variety of Isopropyl-bis(2-picolyl)amine Complexes with Zinc(II) and Copper(II)

Diverse Functionalization of Ruthenium-Chelated 2-Picolylamines: Oxygenation, Dehydrogenation, Cyclization, and N-Dealkylation

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