Controlling chirality in the synthesis of 4 + 4 diastereomeric amine macrocycles derived from<i>trans</i>-1,2-diaminocyclopentane and 2,6-diformylpyridine

Fedorowicz, Dominka; Banach, Sylwia; Koza, Patrycja; Frydrych, Rafał; Ślepokura, Katarzyna; Gregoliński, Janusz

doi:10.1039/d1ob02410h

Cited by 4 publications

(4 citation statements)

References 68 publications

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“…During our synthetic and spectroscopic studies, the [2+2] and [3+3] forms were the major products, with the [4+4] species only detected through mass spectrometry analysis and not isolated in the bulk material. There are reports of metal complexes with [4+4] Schiff base macrocycles, 47,[76][77][78][79][80][81] but only limited examples for trianglimine 82 or isotrianglimine 36 derivatives, the latter of which was characterised crystallographically, however as a mesorather than homochiral structure.…”

Section: Figure 6: (A) Schematic Showing the Crystallisation Conditio...mentioning

confidence: 99%

Dynamic and solid-state behaviour of bromoisotrianglimine

Scholes,

Kershaw-Cook,

Szczypiński

et al. 2023

Preprint

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Solid-state materials formed from discrete imine macrocycles have potential in industrial separations, but dynamic behaviour during both synthesis and crystallisation makes them challenging to exploit. Here, we explore opportunities for structural control by investigating the dynamic nature of a C-5 brominated isotrianglimine in solution and under crystallisation conditions. In solution, the equilibrium between the [3+3] and the less reported [2+2] macrocycle was investigated, and both macrocycles were fully characterised. Solvent templating during crystallisation was used to form new packing motifs for the [3+3] macrocycle and an unreported [4+4] macrocycle. Finally, chiral self-sorting was used to demonstrate how crystallisation conditions can not only influence packing arrangements but also shift the macrocycle equilibrium to yield new structures. This work thus exemplifies three strategies for exploiting dynamic behaviour to form isotrianglimine materials, and highlights the importance of understanding the dynamic behaviour of a system when designing and crystallising functional materials formed using dynamic covalent chemistry.

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Section: Figure 6: (A) Schematic Showing the Crystallisation Conditio...mentioning

confidence: 99%

Dynamic and solid-state behaviour of bromoisotrianglimine

Scholes,

Kershaw-Cook,

Szczypiński

et al. 2023

Preprint

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“…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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“…3,4,10,11,14 Macrocyclic polyamines are obtained from the reduction of parental polyimine compounds, which are produced in the condensation of diamine and dialdehyde substrates. [11][12][13][14][15][16][17] Sometimes their iso-lation requires demetallation if the condensation was run in the presence of a metal template. [18][19][20][21] Many metalla-macrocyclic complexes of high nuclearity have been reported so far, [22][23][24][25] but there have been relatively few examples of reported macrocyclic complexes of high nuclearity.…”

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confidence: 99%

Hexa- and octanuclear copper(ii) complexes with a tetraeicosaaza amine macrocycle

Fedorowicz,

Ślepokura,

Kłak

et al. 2023

Dalton Trans.

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Controlling chirality in the synthesis of 4 + 4 diastereomeric amine macrocycles derived fromtrans-1,2-diaminocyclopentane and 2,6-diformylpyridine

Abstract: A few suitably long dialdehyde and primary diamine building blocks of a predetermined chirality have been designed and synthesized to enable controlled and efficient synthesis of all 6 possible diastereomers...

Cited by 4 publications

References 68 publications

Dynamic and solid-state behaviour of bromoisotrianglimine

Dynamic and solid-state behaviour of bromoisotrianglimine

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

Hexa- and octanuclear copper(ii) complexes with a tetraeicosaaza amine macrocycle

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