Dual reactivity based dynamic covalent chemistry: mechanisms and applications

Abstract

Dynamic covalent chemistry (DCC) focuses on reversible formation, breakage, and exchange of covalent bonds and assemblies, setting a bridge between irreversible organic synthesis and supramolecular chemistry and finding wide utility....

The Dynamic Chemistry of Orthoesters and Trialkoxysilanes: Making Supramolecular Hosts Adaptive, Fluxional, and Degradable

“…13,14 The use of DCvC in supramolecular host−guest chemistry has recently attracted considerable interest. 15,16 Representative examples for additions to the toolbox of DCvC include tetrazines, 17 triazines, 18 (hemi)aminals, 19 amidines, 20 imides, 21 (cyclo)benzoins, 22 carbamates, 23 ureas, 24 dithioacetals, 25 diselenides, 26 alkynes, 27 azines, 28 and even amides. 29 Our group recently explored the exchange reactions of simple (trithio)orthoesters and trialkoxysilanes with alcohols/ thiols.…”

“…Dynamic covalent chemistry (DCvC) combines the dynamic features of supramolecular chemistry with the robustness of covalent bonds, thereby enabling self-assembly processes with error correction. Popular exchange reactions in this area include imine, disulfide, hydrazone, (thio)­ester, and boronic ester exchange. , The unique feature of DCvC, i.e., the reversibility of the underlying transformations, makes it a powerful tool for identifying ligands for medicinally relevant biotargets , or the synthesis of functional materials such as recyclable polymers, , shape-persistent porous cages, , and porous framework materials. , The use of DCvC in supramolecular host–guest chemistry has recently attracted considerable interest. , Representative examples for additions to the toolbox of DCvC include tetrazines, triazines, (hemi)­aminals, amidines, imides, (cyclo)­benzoins, carbamates, ureas, dithioacetals, diselenides, alkynes, azines, and even amides …”

Multiple control of azoquinoline based molecular photoswitches

“…[66][67][68][69][70] Along our longstanding efforts in the ourishing eld of dynamic covalent chemistry (DCC), [71][72][73][74][75][76] we developed a general concept of dual reactivity based DCC through regulating equilibrating tautomers. [77][78][79][80][81][82][83] The selection of reaction pathways allowed the creation of switchable reaction networks, 78,79 discrete assemblies, 80 uorescent materials, 81 as well as dynamic polymers. 82,83 Inspired by the controllable switching patterns and abundant signaling outputs, we propose merging azoquinoline photoswitches and ring-chain tautomerism toward the ultimate goal of multi-responsive and multi-state switching systems (Fig.…”

Kinetic Control of Complexity in Multiple Dynamic Libraries

“…In this case, the same functional group reacts in two different reversible processes, and then, certain building blocks can participate in both libraries, which can then be mutually affected by the other (Figure 1). [43][44][45][46][47][48][49][50][51][52][53][54] All the communications between dynamic libraries reported so far are reversible in nature (Figure 1a): The shared building block can switch from one library to the other in a reversible way. Complexity can then be controlled because, by definition, when one of the libraries increases in size, the other has to decrease, which explains why reversible communication has also been called antiparallel dynamic covalent chemistry.…”