“On-Water” accelerated dearomative cycloaddition via aquaphotocatalysis

Abstract

Sulfur(VI) fluoride exchange (SuFEx) has emerged as an innovative click chemistry to harness the pivotal connectivity of sulfonyl fluorides. Synthesizing such alkylated S(VI) molecules through a straightforward process is of paramount importance, and their water-compatibility opens the door to a plethora of applications in biorelevant and materials chemistry. Prior aquatic endeavors have primarily focused on delivering catalysts involving ionic mechanisms, studies regarding visible-light photocatalytic transformation are unprecedented. Herein we report an on-water accelerated dearomative aquaphotocatalysis for heterocyclic alkyl SuFEx hubs. Notably, water exerts a pronounced accelerating effect on the [2 + 2] cycloaddition between (hetero)arylated ethenesulfonyl fluorides and inert heteroaromatics. This phenomenon is likely due to the high-pressure-like reactivity amplification at the water-oil interface. Conventional solvents proved totally ineffective, leading to the isomerization of the starting material.

Developing water compatible synthetic methods for Sulfur(VI) fluoride exchange (SuFEx) chemistry is of paramount importance. Here the authors demonstrate a catalytic dearomative [2+2] photocycloaddition that significantly speeds up the synthesis of heterocyclic alkyl SuFEx hubs, leveraging the unique reactivity at the water-oil interface.