83706-31-4Relevant academic research and scientific papers
SuFEx Chemistry of Thionyl Tetrafluoride (SOF4) with Organolithium Nucleophiles: Synthesis of Sulfonimidoyl Fluorides, Sulfoximines, Sulfonimidamides, and Sulfonimidates
Gao, Bing,Li, Suhua,Wu, Peng,Moses, John E.,Sharpless, K. Barry
, p. 1939 - 1943 (2018/01/22)
Thionyl tetrafluoride (SOF4) is a valuable connective gas for sulfur fluoride exchange (SuFEx) click chemistry that enables multidimensional linkages to be created via sulfur–oxygen and sulfur–nitrogen bonds. Herein, we expand the available SuFEx chemistry of SOF4 to include organolithium nucleophiles, and demonstrate, for the first time, the controlled projection of sulfur–carbon links at the sulfur center of SOF4-derived iminosulfur oxydifluorides (R1?N=SOF2). This method provides rapid and modular access to sulfonimidoyl fluorides (R1?N=SOFR2), another array of versatile SuFEx connectors with readily tunable reactivity of the S?F handle. Divergent connections derived from these valuable sulfonimidoyl fluoride units are also demonstrated, including the synthesis of sulfoximines, sulfonimidamides, and sulfonimidates.
THIONYL TETRAFLUORIDE MODIFIED COMPOUNDS AND USES
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Page/Page column 79; 80, (2018/06/22)
Thionyl tetrafluoride gas reacts efficiently with primary amines to form reactive iminosulfur oxydifluoride compounds. These dual SVI-F loaded iminosulfur oxydifluoride compounds, in turn, readily react with secondary amines or aryloxy silyl ethers (ArO-SiR3), yielding the corresponding fused heteroatom-linked substrates. Iminosulfur oxyfluoride polymers also are provided by disclosed methods.
A study of the reactivity of S(VI)-F containing warheads with nucleophilic amino-acid side chains under physiological conditions
Mukherjee,Debreczeni,Breed,Tentarelli,Aquila,Dowling,Whitty,Grimster
, p. 9685 - 9695 (2017/11/30)
Sulfonyl fluorides (SFs) have recently emerged as a promising warhead for the targeted covalent modification of proteins. Despite numerous examples of the successful deployment of SFs as covalent probe compounds, a detailed exploration of the factors influencing the stability and reactivity of SFs has not yet appeared. In this work we present an extensive study on the influence of steric and electronic factors on the reactivity and stability of the SF and related SVI-F groups. While SFs react rapidly with N-acetylcysteine, the resulting adducts were found to be unstable, rendering SFs inappropriate for the durable covalent inhibition of cysteine residues. In contrast, SFs afforded stable adducts with both N-acetyltyrosine and N-acetyllysine; furthermore, we show that the reactivity of arylsulfonyl fluorides towards these nucleophilic amino acids can be predictably modulated by adjusting the electronic properties of the warhead. These trends were largely conserved when the covalent reaction occurred within a protein binding pocket. We have also obtained a crystal structure depicting covalent modification of the catalytic lysine of a tyrosine kinase (FGFR1) by the ATP analog 5′-O-3-((fluorosulfonyl)benzoyl)adenosine (m-FSBA). Highly reactive warheads were demonstrated to be unstable with respect to hydrolysis in buffered aqueous solutions, indicating that warhead reactivity must be carefully tuned to provide optimal rates of protein modification. Our results demonstrate that the reactivity of SFs complements that of more commonly studied acrylamides, and we hope that this work spurs the rational design of novel SF-containing covalent probe compounds and inhibitors, particularly in cases where a suitably positioned cysteine residue is not present.
Preparation and Reactions of Sulfonimidoyl Fluorides
Johnson, Carl R.,Bis, Kostaki G.,Cantillo, Jose H.,Meanwell, Nicholas A.,Reinhard, Michael F. D.,et al.
, p. 1 - 3 (2007/10/02)
Sulfonimidoyl fluorides have been prepared for the first time by treatment of sulfonimidoyl chlorides with various sources of fluoride ion.Sulfonimidoyl chlorides are reduced to sulfinamides with alkyllithium reagents; however, the corresponding fluorides
