A New Synthetic Strategy Leading to Homochiral Macrocycles Derived from 2,6‐Diformylpyridine and (1S,2S)‐trans‐1,2‐Diaminocyclopentane

Gregoliński, Janusz; Ślepokura, Katarzyna; Bil, Andrzej; Lisowski, Jerzy

doi:10.1002/ejoc.202000919

Cited by 9 publications

(14 citation statements)

References 59 publications

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“…These parameters are also comparable to those of two different tetraammonium (H 4 L) 4+ species, namely [H 4 L](NO 3 ) 4 •(CSD_ZUVKUW) [21] and [H 4 L]Br 4 •H 2 O (CSD_ZIVPAV) [22]. They are also in the range of those found for other tetraprotonated related ligands such as [H 4 L Me2 ](NO 3 ) 4 (CSD_DIJZOO) [4], [26], and [H 4 L cyp2 ]Cl 4 •6.2H 2 O (CSD_HUVYOP) [27]. Likewise, diprotonated species such as [H 2 L cyp2 ]Cl 2 (CSD_EDEWIW) [28], or [H 2 L Me4a ](NO 3 ) 2 (CSD_SICCIR) [8] also show comparable geometric data.…”

Section: X-ray Diffraction Studiesmentioning

confidence: 71%

Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes

Corredoira-Vázquez,

González-Barreira,

Sanmartín-Matalobos

et al. 2024

IJMS

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Hexaazamacrocyclic Schiff bases have been extensively combined with lanthanoid (Ln) ions to obtain complexes with a highly axial geometry. However, the use of flexible hexaazatetraamine macrocycles containing two pyridines and acyclic spacers is rather uncommon. Accordingly, we obtained [DyL(OAc)2]OAc·7H2O·EtOH and [DyLMe2(Cl)2]Cl·2H2O, where L and LMe2 are the 18-membered macrocycles 3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane and 3,10-dimethyl-3,6,10,13-tetraaza-1,8(2,6)-dipyridinacyclotetradecaphane, respectively, which contain ethylene and methylethylene spacers between their N3 moieties. [DyL(OAc)2]OAc·7H2O·EtOH represents the first crystallographically characterized lanthanoid complex of L, while [DyLMe2(Cl)2]Cl·2H2O contributes to increasing the scarce number of LnIII compounds containing LMe2. Furthermore, the crystal structure of L·12H2O was solved, and it was compared with those of other related macrocycles previously published. Likewise, the crystal structures of the DyIII complexes were compared with those of the lanthanoid and d-metal complexes of other 18-membered N6 donor macrocycles. This comparison showed some effect of the spacers employed, as well as the influence of the size of the ancillary ligands and the metal ion. Additionally, the distinct folding behaviors of these macrocycles influenced their coordination geometries. Moreover, the luminescent properties of [DyL(OAc)2]OAc·7H2O·EtOH and [DyLMe2(Cl)2]Cl·2H2O were also investigated, showing that both complexes are fluorescent, with the emission being sensitized by the ligands.

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Section: X-ray Diffraction Studiesmentioning

confidence: 71%

Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes

Corredoira-Vázquez,

González-Barreira,

Sanmartín-Matalobos

et al. 2024

IJMS

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“…Amine 55 (all-(S) enantiomer), which is a homochiral isomer of amine 54, may be isolated in small (5.6 %) yields by using gel permeation chromatography from the mixture of macrocyclic amines which are obtained by the reduction of the mixture of imines resulting from the condensation of enantiopure DACP and DFP (the main product being the [3 + 3] macrocycle). Alternatively, amine 55 may be obtained in high (52.2 %) yield in step-wise synthesis from the intermediate 56 and DFP [123]. Apart from meso amine 54 of RRSSRRSS chirality of diaminocyclohexane fragments and its homochiral isomer 55 of SSSSSSSS chirality, other isomers of RRRRSSSS (achiral) and RRRRRRSS (enantiopure) chirality may be obtained in step-wise synthesis via protection/deprotection strategy of linear intermediates [124].…”

Section: [4 + 4] Macrocyclesmentioning

confidence: 99%

Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes

Lisowski

2022

Molecules

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The condensation of aromatic dialdehydes with chiral diamines, such as 1,2-trans-diaminocyclohexane, leads to various enantiopure or meso-type macrocyclic Schiff bases, including [2 + 2], [3 + 3], [4 + 4], [6 + 6] and [8 + 8] condensation products. Unlike most cases of macrocycle synthesis, the [3 + 3] macrocycles of this type are sometimes obtained in high yields by direct condensation without a metal template. Macrocycles of other sizes from this family can often be selectively obtained in high yields by a suitable choice of metal template, solvent, or chirality of the building blocks. In particular, the application of a cadmium(II) template results in the expansion of the [2 + 2] macrocycles into giant [6 + 6] and [8 + 8] macrocycles. These imine macrocycles can be reduced to the corresponding macrocyclic amines which can act as hosts for the binding of multiple cations or multiple anions.

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“…The other situation can be observed in the condensation of enantiomerically pure trans -1,2-diaminocyclopentane ( 155 ) with 2,6-diformylpyridine ( 156 ) in methanol [ 54 ]. Reduction of the mixture of imine products results in the mixture of [2 + 2], [3 + 3], [4 + 4] and [5 + 5] macrocyclic amines 157 – 160 , which can be separated to yield small amount of new [4 + 4] and [5 + 5] products ( Figure 32 ).…”

Section: Nitrogen-containing Macrocycles—applicationsmentioning

confidence: 99%

Recent Advances in the Synthesis and Applications of Nitrogen-Containing Macrocycles

Grajewski

2022

Molecules

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Macrocyclic nitrogen-containing compounds are versatile molecules. Supramolecular, noncovalent interactions of these macrocycles with guest molecules enables them to act as catalysts, fluorescent sensors, chiral or nonchiral selectors, or receptors of small molecules. In the solid state, they often display a propensity to form inclusion compounds. All of these properties are usually closely connected with the presence of nitrogen atoms in the macrocyclic ring. As most of the reviews published so far on macrocycles were written from the viewpoint of functional groups, synthetic methods, or the structure, search methods for literature reports in terms of the physicochemical properties of these compounds may be unobvious. In this minireview, the emphasis was put on the synthesis and applications of nitrogen-containing macrocyclic compounds, as they differ from their acyclic analogs, and at the same time are the driving force for further research.

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A New Synthetic Strategy Leading to Homochiral Macrocycles Derived from 2,6‐Diformylpyridine and (1S,2S)‐trans‐1,2‐Diaminocyclopentane

Cited by 9 publications

References 59 publications

Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes

Exploring the Spatial Arrangement of Simple 18-Membered Hexaazatetraamine Macrocyclic Ligands in Their Metal Complexes

Imine- and Amine-Type Macrocycles Derived from Chiral Diamines and Aromatic Dialdehydes

Recent Advances in the Synthesis and Applications of Nitrogen-Containing Macrocycles

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