Dynamic Multicomponent Hemiaminal Assembly

Reversible covalent bonding is often employed for the creation of novel supramolecular structures, multi-component assemblies, and sensing ensembles. In spite of remarkable success of dynamic covalent systems, the reversible binding of a mono-alcohol with high strength is challenging. Here we show that a strategy of carbonyl activation and hemiaminal ether stabilization can be embodied in a four-component reversible assembly that creates a tetradentate ligand and incorporates secondary alcohols with exceptionally high affinity. Evidence is presented that the intermediate leading to binding and exchange of alcohols is an iminium ion. Further, to demonstrate the use of this assembly process we explored chirality sensing and enantiomeric excess determinations. An induced twist in the ligand by a chiral mono-ol results in large Cotton effects in the circular dichroism spectra indicative of the alcohol’s handedness. The strategy revealed in this study should prove broadly applicable for the incorporation of alcohols into supramolecular architecture construction.

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“…1b 39 . We reasoned that if the product of this reaction ( 2 ) could be induced to eliminate water, iminium ion 3 would form.…”

Section: Resultsmentioning

confidence: 99%

Dynamic multi-component covalent assembly for the reversible binding of secondary alcohols and chirality sensing

2011

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“…The tetrahedral carbinolamine group can be stabilized also by metal ions. Nitrogen-containing aromatic heterocyclic aldehydes react with di-(2-picolyl)amine in presence of Zn 2+ salts to form labile tris-(2-picolyl) hemiaminal zinc complexes [22]. Rhodium (III) complexes of o-diphenylphosphinobenzaldehyde react with dihydrazones to give ionic species with a new tridentate PNN-hemiaminal type ligand [23].…”

Section: Open Accessmentioning

confidence: 99%

A Study on the Condensation Reaction of 4-Amino-3,5-dimethyl-1,2,4-triazole with Benzaldehydes: Structure and Spectroscopic Properties of Some New Stable Hemiaminals

Wajda-Hermanowicz¹,

Pieniążczak²,

Zatajska³

et al. 2015

Molecules

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Studies on the stable hemiaminals and Schiff bases formation in the reaction of substituted benzaldehydes with primary 3,5-dimethyl-1,2,4-triazole 4-amine were carried out under neutral conditions. These products were investigated by IR, Raman, MS, 1 H-and 13 C-NMR spectra as well as by X-ray crystallography. The effect of reaction conditions: temperature, polarity of the solvents utilized, substrate concentration and the ortho and para benzaldehyde substituents on the yield of products was also examined.

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“…Recently, the first example of an anion‐controlled metal‐templated synthesis of an aminal–(bis)imine Fe II complex was reported . Again, aminal‐ and hemiaminal‐based dynamic combinatorial libraries (DCLs) have been developed through Zn II ‐templated reactions . Herein, we report an example for which metal‐templated sub‐component self‐assembly fails.…”

Section: Introductionmentioning

confidence: 97%

Hampered Subcomponent Self‐Assembly Leads to an Aminal Ligand: Reactivity with Silver(I) and Copper(II)

et al. 2016

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Insight into the ineffectiveness of a subcomponent self‐assembly procedure between 4‐aminopyridine (4‐apy) and pyridine‐2‐carbaldehyde (2‐pyA) led to a new aminal ligand (L). The combination of L with AgI gave a 2D luminescent network, in which the silver ions have a distorted triangular‐pyramidal coordination geometry. The aminal is stable in acetonitrile and DMSO but decomposes in alcohol solvents. Moreover, we found that CuII also induced the decomposition of L, which led to Cu(pic)2, {[Cu(4‐apy)4](ClO4)2}, and an unprecedented {[Cu4(pic)4(OH)2(H2O)6](ClO4)2} tetramer based on CuII ions and picolinic acid (Hpic) generated in situ. The decomposition pathway of L was clarified by a combination of single‐crystal XRD analysis, NMR spectroscopy, and ESI‐MS.

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Dynamic Multicomponent Hemiaminal Assembly

Cited by 49 publications

References 57 publications

Dynamic multi-component covalent assembly for the reversible binding of secondary alcohols and chirality sensing

Dynamic multi-component covalent assembly for the reversible binding of secondary alcohols and chirality sensing

A Study on the Condensation Reaction of 4-Amino-3,5-dimethyl-1,2,4-triazole with Benzaldehydes: Structure and Spectroscopic Properties of Some New Stable Hemiaminals

Hampered Subcomponent Self‐Assembly Leads to an Aminal Ligand: Reactivity with Silver(I) and Copper(II)

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