Interaction of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion

Reactions of 2,4,6-tris(fluorosulfonyl)chlorobenzene 1 with O-, N-, S-, C-nucleophiles and F-anion showed high reactivity of 1 that was defined by three strong electron withdrawing SO2F groups creating several electrophilic centers within the molecule. Conditions for selective chlorine atom substitution were defined that resulted in formation of corresponding ethers, amines and sulfides, while excess of nucleophile commonly led to SO2F groups implication in the reaction. Two equivalents of fluoride-anion source gave rise not only to the chlorine-fluorine substitution but afforded in the anionic σ-complex formation with two fluorine atoms in the hem-position. Reduction of chlorobenzene 1 with zinc/AcOH was found to be a choice for 1,3,5-tris(fluorosulfonyl)benzene preparation.

Graphical abstractReactions of 2,4,6-tris(fluorosulfonyl)chlorobenzene with O-, N-, S-, C-nucleophiles and F-anion showed high reactivity of chlorine atom defined by three strong electron withdrawing SO2F groups. Conditions for selective Cl atom substitution were found out that resulted in formation of corresponding ethers, amines and sulfides, while excess of nucleophile commonly led to SO2F groups implication in the reaction. Two equivalents of fluoride-anion source gave rise not only to the chlorine-fluorine substitution but afforded in the anionic σ-complex formation with two fluorine atoms in the hem-position. Reduction by zinc/AcOH was found to be a choice for 1,3,5-tris(fluorosulfonyl)benzene convenient preparation.Figure optionsDownload full-size imageDownload as PowerPoint slideHighlights► Selective reactions of 2,4,6-tris(fluorosulfonyl)chlorobenzene with a O-, N-, S-, C-nucleophiles. ► Excess of nucleophile commonly led to SO2F groups implication in the reaction. ► Fluoride-anion source gave anionic σ-complex with two fluorine atoms in the hem-position. ► Reduction with zinc/AcOH conveniently led to 1,3,5-tris(fluorosulfonyl)benzene.