Sulfur in Dynamic Covalent Chemistry

Abstract

Sulfur has been important in dynamic covalent chemistry (DCC) since the beginning of the field. Mainly as part of disulfides and thioesters, dynamic sulfur-based bonds (DSBs) have a leading role in several remarkable reactions. Part of this success is due to the almost ideal properties of DSBs for the preparation of dynamic covalent systems, including high reactivity and good reversibility under mild aqueous conditions, the possibility of exploiting supramolecular interactions, access to isolable structures, and easy experimental control to turn the reaction on/off. DCC is currently witnessing an increase in the importance of DSBs. The chemical flexibility offered by DSBs opens the door to multiple applications. This Review presents an overview of all the DSBs used in DCC, their applications, and remarks on the interesting properties that they confer on dynamic chemical systems, especially those containing several DSBs.

Dynamic Covalent Chemistry for Synthesis and Co‐conformational Control of Mechanically Interlocked Molecules

“…Disulfides are complementary to imines by enabling dynamic exchange under basic conditions, but remaining inert in acidic environments. [12] Consequently, dynamic disulfide exchange has also proven efficient for MIM creation, in particular in aqueous media. However, an important difference to imines is the symmetry of the exchange -imines have directionality and are composed of two different functional groups coming together, Figure 3.…”

“…[9] Dynamic covalent chemistry uses reversible covalent bonds to access the local thermodynamic minima for a given assembly of starting materials, i. e. the structure with the lowest free energy dominates. [10][11][12][13] Since compounds formed through dynamic covalent chemistry represent thermodynamic products, the assembly efficiency is usually high and excellent yields and selectivities can be obtained even for complex products. The reversibility of the linkages provides proof-reading and error-correction to the structural assembly, enabling kinetic products to gradually disassemble and reassemble into the desired thermodynamic product.…”

“…Dynamic covalent chemistry uses reversible covalent bonds to access the local thermodynamic minima for a given assembly of starting materials, i. e. the structure with the lowest free energy dominates [10–13] . Since compounds formed through dynamic covalent chemistry represent thermodynamic products, the assembly efficiency is usually high and excellent yields and selectivities can be obtained even for complex products.…”

Stress‐Induced Shape‐Shifting Materials Possessing Autonomous Self‐Healing and Scratch‐Resistant Ability

“…Thia-Michael adduct is another powerful dynamic linkage in the extensive list of dynamic covalent linkages, [54] which is categorized among the Click reactions owing to its modular nature. [55][56][57] The chemistry is strongly utilized in polymer chemistry to develop CANs, hydrogels, [58] post synthesis functionalization, [59,60] and tagging purposes. [61,62] Typically, an organic base in form of the amine compounds is utilized to facilitate the rate of thia Michael adduct formation.…”

Generic Recycling Strategy to Improve Robustness of Recycled Rubbers through Bioinspired Multiphase Network

“…To construct an effective multiphase network through virgin rubber and WR, our group considers that improving the interface interaction between virgin rubber and WR is extraordinarily important, as shown in Figure . In the sulfur cross-linking network, S–S cross-links often exhibit dynamic characteristics . Through the S–S dynamic characteristics, we can construct the interface interaction between virgin rubber and WR.…”