Ex situ Generation of Thiazyl Trifluoride (NSF₃) as a Gaseous SuFEx Hub**

Abstract

Sulfur(VI)-fluoride exchange (SuFEx) chemistry, an all-encompassing term for substitution events that replace fluoride at an electrophilic sulfur(VI), enables the rapid and flexible assembly of linkages around a S VI core. Although a myriad of nucleophiles and applications works very well with the SuFEx concept, the electrophile design has remained largely SO 2 -based. Here, we introduce S�N-based fluorosulfur(VI) reagents to the realm of SuFEx chemistry. Thiazyl trifluoride (NSF 3 ) gas is shown to serve as an excellent parent compound and SuFEx hub to efficiently synthesize mono-and disubstituted fluorothiazynes in an ex situ generation workflow. Gaseous NSF 3 was evolved from commercial reagents in a nearly quantitative fashion at ambient conditions. Moreover, the mono-substituted thiazynes could be extended further as SuFEx handles and be engaged in the synthesis of unsymmetrically disubstituted thiazynes. These results provide valuable insights into the versatility of these understudied sulfur functionalities paving the way for future applications.

Perfluorooxosulfate Salts as SOF4‐Gas‐Free Precursors to Multidimensional SuFEx Electrophiles

“…In 2014, Sharpless established this branch of click chemistry by exploring the distinctive chemical behavior of sulfonyl fluorides (R−SO 2 F) and fluorosulfates (R−OSO 2 F) [3] . Later also sulfurimidoyl fluoride (RN=SOF 2 ) [4] and thiazyl fluoride (NSF 3 ) [5] compounds were added, a remarkable advancement by merit of their multiple‐bonded azasulfur(VI) moiety and multiple interchangeable S−F bonds which easily undergo consecutive nucleophilic exchange (Scheme 1B). A small but growing number of studies has explored the chemistry of [N=S=O]‐based SuFExable compounds, unveiling intriguing reactivity patterns across diverse applications from small molecules [6] to bioconjugation [4a,7] and polymers [8]…”

Intramolecular Chalcogen Bonding Activated SuFEx Click Chemistry for Efficient Organic-Inorganic Linking

“…The important role of click chemistry in modern science has been recognized by the 2022 Nobel Prize in Chemistry 1,2 . Recently, a new generation of click chemistry, sulfur uoride exchange (SuFEx) promoted by Sharpless, Moses and co-workers, has demonstrated impressive molecular assembly capabilities [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17] .…”

“…Bene ted from the diverse collection of SuFExable hubs 3,[7][8][9][10][11][12][13][14] , SuFEx chemistries offer tremendous scope for exploring chemical space and wide range of sulfuryl-heteroatom connectors to meet more diverse linking needs, thus enabling its rapid development as the technology of choice in organic synthesis [18][19][20] , drug discovery [21][22][23] , chemical biology 24,25 and polymer chemistry [26][27][28] (Fig. 1a).…”