Introduction of axial chirality at a spiro carbon atom in the synthesis of pentaerythritol–imine macrocycles

Grajewski, Jakub; Piotrowska, Kamila; Zgorzelak, Mikołaj; Janiak, Agnieszka; Biniek-Antosiak, Katarzyna; Rychłewska, Urszula; Gawroński, Jacek

doi:10.1039/c7ob02672b

Cited by 8 publications

(5 citation statements)

References 45 publications

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“…In both 5 and 6 the characteristic pattern of CE can be observed and it is an evidence of diequatorial positions of C=N bonds in the cyclohexane rings. Similar pattern of CE can be observed in all ( R , R )‐DACH based macrocyclic polyimines and reflects a negative helicity of the vicinal imine bonds in both macrocycles [1a,3c,d,5a] . The tables with Δϵ and ϵ values for both compounds can be found in SI.…”

Section: Resultssupporting

confidence: 61%

Controlled, Sunlight‐Driven Reversible Cycloaddition of Multiple Singlet Oxygen Molecules to Anthracene‐Containing Trianglimine Macrocycles

et al. 2022

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Controlled release of singlet oxygen is of interest not only to chemists, but also to biologists and medics involved in cancer therapy. Two chiral polyaza macrocyclic compounds and their corresponding endoperoxides have been synthesized. These peroxides exhibit high temperature stability, up to 80 °C. Detailed studies on their structure, including X‐ray analysis as well as NMR, UV‐VIS ECD spectroscopy and theoretical calculations, combined with photochemical measurements indicate that their high stability is related to the arrangement of oxygen atoms in a conformationally stable macrocyclic ring. Despite the change of carbon hybridization from sp2 to sp3 at the 9 and 10 positions of the anthracene units, the macrocyclic skeleton of the obtained compounds does not change its conformation. The obtained endoperoxides can be formed and release singlet oxygen by irradiation with UV light of 365 and 275 nm, respectively. Release of the oxygen does not degrade the macrocyclic structure.

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Section: Resultssupporting

confidence: 61%

Controlled, Sunlight‐Driven Reversible Cycloaddition of Multiple Singlet Oxygen Molecules to Anthracene‐Containing Trianglimine Macrocycles

et al. 2022

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“…The formation of [2 + 2] imines is preferred when enantiopure DACH is condensed with dialdehydes based on two benzaldehyde fragments that are connected by a link X (Figure 9) which enforces the bent conformation of the dialdehyde. Because of the resulting shape of the macrocycle, these products were called rhombimines (Figure 9) [56][57][58][59][60]. The reduced form of this kind of macrocycles, i.e., rhombamines was applied in NMR The formation of [2 + 2] imines is preferred when enantiopure DACH is condensed with dialdehydes based on two benzaldehyde fragments that are connected by a link X (Figure 9) which enforces the bent conformation of the dialdehyde.…”

Section: [2 + 2] Macrocyclesmentioning

confidence: 99%

“…The reduced form of this kind of macrocycles, i.e., rhombamines was applied in NMR The formation of [2 + 2] imines is preferred when enantiopure DACH is condensed with dialdehydes based on two benzaldehyde fragments that are connected by a link X (Figure 9) which enforces the bent conformation of the dialdehyde. Because of the resulting shape of the macrocycle, these products were called rhombimines (Figure 9) [56][57][58][59][60]. The reduced form of this kind of macrocycles, i.e., rhombamines was applied in NMR enantiodiscrimination of chiral carboxylic acids and their derivatives [61,62].…”

Section: [2 + 2] 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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“…Polyimine macrocycles were also used for the introduction of axial chirality at a spiro carbon in a macrocycle ring [ 48 ]. The key step for the synthesis was the formation of an axial chirality in a quaternary carbon atom having four constitutionally identical substituents.…”

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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Introduction of axial chirality at a spiro carbon atom in the synthesis of pentaerythritol–imine macrocycles

Cited by 8 publications

References 45 publications

Controlled, Sunlight‐Driven Reversible Cycloaddition of Multiple Singlet Oxygen Molecules to Anthracene‐Containing Trianglimine Macrocycles

Controlled, Sunlight‐Driven Reversible Cycloaddition of Multiple Singlet Oxygen Molecules to Anthracene‐Containing Trianglimine Macrocycles

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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