Self‐Assembly in Systems of Subcomponents: Simple Rules, Subtle Consequences

Simultaneous Disulfide and Boronic Acid Ester Exchange in Dynamic Combinatorial Libraries

“…Disulfide exchange [ 5 ], hydrazone exchange [ 6 ] and imine exchange [ 7 ] are amongst the most extensively utilized reactions in dynamic combinatorial chemistry. If two or more reversible reactions can be engineered into DCLs the structural diversity of the library increases dramatically [ 8 , 9 , 10 , 11 , 12 , 13 , 14 , 15 , 16 , 17 , 18 , 19 , 20 ]. In a DCL that makes use of two different reversible reactions, the reactions may be: (1) addressed simultaneously, where the reactions are reversible under the same reaction conditions; or (2) addressed orthogonally, where the two reactions are only reversible under different conditions.…”

Complex Systems from Simple Building Blocks via Subcomponent Self-Assembly

“…15,[26][27][28] Sorting: we have employed the techniques and ideas of dynamic combinatorial chemistry 6,29,30 to study the parameters that allow complex dynamic combinatorial libraries (DCLs), consisting of mixtures of structures that interconvert through the exchange of subcomponents, to be sorted by taking advantage of the thermodynamic preferences of the system. 24,27,30,31 Systems chemistry: we have extended the ideas of reconfiguration and sorting to study the interplay between separate reversible chemistries, 32,33 allowing entry into the emerging area of systems chemistry. [32][33][34][35] Chiral communication: we have investigated chiral information transfer within systems containing both fixed (carbon stereocenters) and dynamic (metal stereocenters) chirality; 30,36 the possibility of exchanging chiral elements between structures provides additional complexity and interest.…”

Kinetic and Thermodynamic Self-Sorting in Synthetic Systems

“…ture from expressing an otherwise favorable interaction in another. 11 Self-sorting should be distinguished from the related process of self-assembly: while the latter reduces a complex mixture of precursors into a single species with high fidelity, the former produces a system of several species (also with high fidelity). 10a Thermodynamic self-sorting relies on the reversibility of the interactions between components to achieve error correction as the system approaches equilibrium.…”

“…Stang et al have recently demonstrated self-sorting induced entirely by secondary effects, such as hydrophobicity of pendant groups not involved in metalligand coordination. 29 Nitschke's group has reported a series of elegant studies 11,30 wherein self-sorting of imine complexes with metals (typically Cu + or Fe 2+ ) is achieved by combining two dynamic reactions: imine metathesis and metalligand exchange. Self-sorting in these systems can be regulated with external stimuli, such as metal or ligand exchange, 30a or even through simple changes in stoichiometries of reacting partners (Scheme 3).…”

“…Self-sorting in these systems can be regulated with external stimuli, such as metal or ligand exchange, 30a or even through simple changes in stoichiometries of reacting partners (Scheme 3). 11 Thus, a set of four constituents P-S could be used to express different Cu + -imine complexes 16-18 (Scheme 3). Authors likened the set of rules that drives this process to a primitive programming language, wherein molecular inputs translate into supramolecular outputs.…”