Competition-driven selection in covalent dynamic networks and implementation in organic reactional selectivity

Kovaříček, Petr; Meister, Anne C.; Flídrová, Karolína; Cabot, Rafel; Kovaříčková, K.; Lehn, Jean‐Maríe

doi:10.1039/c5sc04924e

Cited by 27 publications

(30 citation statements)

References 88 publications

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“…Such competitive processes generate mixed DCLs, containing different types of C=N compounds, which undergo variations in imine product distribution as a function of time, depending on the relative reaction rates and imine stabilities. Such experiments also allow for the exploration of selectivity in derivatization and dynamic protection of molecules possessing different amino groups in order to select different products based on either kinetic or thermodynamic features …”

Section: Introductionmentioning

confidence: 99%

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry

Kulchat

Chaur

Lehn

2017

Chemistry A European J

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The kinetic and thermodynamic selectivities of imine formation have been investigated for several dynamic covalent libraries of aldehydes and amines. Two systems were examined, involving the reaction of different types of primary amino groups (aliphatic amines, alkoxy-amines, hydrazides and hydrazines) with two types of aldehydes, sulfobenzaldehyde and pyridoxal phosphate in aqueous solution at different pD (5.0, 8.5, 11.4) on one hand, 2-pyridinecarboxaldehyde and salicylaldehyde in organic solvents on the other hand. The reactions were performed separately for given amine/aldehyde pairs as well as in competitive conditions between an aldehyde and a mixture of amines. In the latter case, the time evolution of the dynamic covalent libraries generated was followed, taking into consideration the operation of both kinetic and thermodynamic selectivities. The results showed that, in aqueous solution, the imine of the aliphatic amine was not stable, but oxime and hydrazone formed well in a pH dependent way. On the other hand, in organic solvents, the kinetic product was the imine derived from an aliphatic amine and the thermodynamic products were oxime and hydrazone. The insights gained from these experiments provide a basis for the implementation of imine formation in selective derivatization of mono-amines in mixtures as well as of polyfunctional compounds presenting different types of amino groups. They may in principle be extended to other dynamic covalent chemistry systems.

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Section: Introductionmentioning

confidence: 99%

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry

Kulchat

Chaur

Lehn

2017

Chemistry A European J

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“…Components 1 , 2 , 5 , and 6 must be trapped into the more stable Fe II and Zn II complexes to allow for the formation of [Cu( 3 , 4 ) 2 ] + . This example demonstrates how CDNs can be leveraged to enforce the formation of thermodynamically unfavorable products …”

Section: Resultsmentioning

confidence: 94%

“…From a more general perspective, the reduction in the diversity of metal complexes formed upon addition of Fe II and Zn II cations to the library of six components 1 – 6 compared to their addition to the library of four components 1 , 2 , 5 , and 6 (see results and discussion above) exemplifies the concept of “simplexity”, namely that an increase in the compositional complexity of a system (i.e. a larger number of components) may lead to a simplified output through dynamic competition …”

Section: Resultsmentioning

confidence: 99%

Triple Self‐Sorting in Constitutional Dynamic Networks: Parallel Generation of Imine‐Based Cu^I, Fe^II, and Zn^II Complexes

2020

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Three imine‐based metal complexes, having no overlap in terms of their compositions, have been simultaneously generated from the self‐sorting of a constitutional dynamic library (CDL) containing three amines, three aldehydes, and three metal salts. The hierarchical ordering of the stability of the three metal complexes assembled and the leveraging of the antagonistic and agonistic relationships existing between the constituents within the constitutional dynamic network corresponding to the CDL were pivotal in achieving the sorting. Examination of the process by NMR spectroscopy showed that the self‐sorting of the FeII and ZnII complexes depended on an interplay between the thermodynamic driving forces and a kinetic trap involved in their assembly. These results also exemplify the concept of “simplexity”—the fact that the output of a self‐assembling system may be simplified by increasing its initial compositional complexity—as the two complexes could self‐sort only in the presence of the third pair of organic components, those of the CuI complex.

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“…Hypothesis and design 2-Formylbenzoic acid exists in the ring form (1, Fig. 1e), [73][74][75][76] with ring/chain tautomerization further dependent on imine formation (2, Fig. 1e).…”

Section: Resultsmentioning

confidence: 99%

n → π* interactions as a versatile tool for controlling dynamic imine chemistry in both organic and aqueous media

Chen

Yun

et al. 2020

Chem. Sci.

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Competition-driven selection in covalent dynamic networks and implementation in organic reactional selectivity

Abstract: Competition among reagents in dynamic combinatorial libraries of increased complexity leads to reactional self-sorting. This fundamental principle allowed development of selective dynamic protecting groups for controlled sequential derivatization of polyamines.

Cited by 27 publications

References 88 publications

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry

Triple Self‐Sorting in Constitutional Dynamic Networks: Parallel Generation of Imine‐Based Cu^I, Fe^II, and Zn^II Complexes

n → π* interactions as a versatile tool for controlling dynamic imine chemistry in both organic and aqueous media

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Competition-driven selection in covalent dynamic networks and implementation in organic reactional selectivity

Abstract: Competition among reagents in dynamic combinatorial libraries of increased complexity leads to reactional self-sorting. This fundamental principle allowed development of selective dynamic protecting groups for controlled sequential derivatization of polyamines.

Cited by 27 publications

References 88 publications

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry

Kinetic Selectivity and Thermodynamic Features of Competitive Imine Formation in Dynamic Covalent Chemistry

Triple Self‐Sorting in Constitutional Dynamic Networks: Parallel Generation of Imine‐Based CuI, FeII, and ZnII Complexes

n → π* interactions as a versatile tool for controlling dynamic imine chemistry in both organic and aqueous media

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Product

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Triple Self‐Sorting in Constitutional Dynamic Networks: Parallel Generation of Imine‐Based Cu^I, Fe^II, and Zn^II Complexes