Adsorption‐Driven Self‐Sorting of Dynamic Imine Libraries

Abstract

Differences in adsorption among the components of complex mixtures play a role in separations, surface-based sensing, and heterogeneous catalysis, and have been implicated in theories of the origin of life. Herein, we consider mixtures of imines and we show that if such complex mixtures are also dynamic-that is, if their components equilibrate among themselves-then they can dramatically simplify in composition during the course of column chromatography. As they travel down the column, imines continuously trade their aldehyde and amine constituents, favoring the formation of molecules with extremes of polarity at the expense of species with intermediate polarities. Iterative application of this principle leads to simplification of imine libraries containing up to 16 members into 4 major products.

Chiral Self‐Sorting of [2+3] Salicylimine Cage Compounds

“…The self-sorting of multicomponent mixtures is aw idely investigated phenomenon in supramolecular, [1] coordination, [2] and dynamic covalent chemistry [3] as it allows either the construction of intricate structures in as ingle step from simple components [4] or the separation of libraries of discrete products. [5] Among self-sorting processes,the self-discrimination (social self-sorting) [6] and self-recognition (narcissistic self-sorting) [7] of enantiomers from racemic mixtures are especially challenging as only the spatial molecular orientations of the enantiomers are different. [3c] While chiral selfsorting of racemic mixtures is well known to occur in the solid state,i ti sf ar more demanding in solution because of the absence of strong bias favoring either homochiral or heterochiral products.…”

Dynamic Nucleophilic Aromatic Substitution of Tetrazines

“…Interestingly, when an intramolecular IEDDA reaction is possible, such as in compound 6‐Tz‐6 , then heating the mixture gives the corresponding diazine ( 6‐Dz ) in 96 % yield, which concomitantly implies that an irreversible self‐inhibition of the exchange can be triggered by high temperatures. This property might be used for the kinetic control of the dynamic libraries of compounds obtained [83–88] …”

A Kinetic Self‐Sorting Approach to Heterocircuit [3]Rotaxanes

“…Self‐sorting reactions typically operate under thermodynamic control, allowing the system to correct errors, although the trajectory to achieve equilibrium can be kinetically complex ,. In keeping with this, previous reports of self‐sorting [ n ]rotaxane synthesis rely on passive templates to direct the assembly of a thermodynamically preferred pseudorotaxane complex before covalent bond formation kinetically traps the interlocked assembly.…”