Among known click chemistry, sulfur (VI) fluoride exchange (SuFEx) reaction is a new generation of click chemistry, in which the S–F bond reacts readily with silyl-protected phenols, phenolates or amines. In 2019, Han Zuilhof’s group discovered that SuFEx reaction is intrinsically an enantiospecific click reaction as a chiral S(VI) center reacts exclusively with inversion of configuration. The SuFEx reaction has also been successfully applied to polymer science with the efficient formation of polymers. In parallel, materials chemistry has been revolutionized by dynamic covalent chemistry (DCC), which combines the strength of covalent bonds with the power for self-healing and responsiveness that is for example displayed in supramolecular chemistry. Unlike other click chemistries, which have demonstrated to allow DCC to occur (like thiol-yne and Diels-Alder reactions), DCC has not been shown for the SuFEx reaction.
Figure 1. a) General scheme for sulfur (VI) phenolate exchange reaction, and facets under current study. b) Degradation of polysulfonimidates.
This paper describes the first case of a SuFEx-derived DCC reaction via the development of Sulfur-Phenolate Exchange (SuPhenEx) reactions, which displays enantiospecificity, wide scope, high efficiency and excellent functional group tolerance. This reaction also allows the construction of two sulfonimidate enantiomers from a single sulfonimidoyl fluoride enantiomer. Finally, SuPhenEx chemistry demonstrates the usefulness of the structurally complex, stable, yet also degradable polymer.
Relevant research has been published in Angwandte Chemie International Edition, with Tianjin University as the first-author institution. This work is mainly finished by Yang Chao and Akash Krishna of SPST. The corresponding author is Prof. Han Zuilhof. The work is strongly supported by all staff of the Instrumental Analytical Center, SPST, Tianjin University and Wageningen University.
The paper link: https://onlinelibrary.wiley.com/doi/10.1002/anie.202207456
By School of Pharmaceutical Science and Technology
Editor: Sun Xiaofang, Wang Jingnan
