The advent of sulfur(vi)-fluoride exchange (SuFEx) processes as transformations with click-like reactivity has invigorated research into electrophilic species featuring a sulfur–fluorine bond. Among these, sulfonyl fluorides have emerged as the workhorse functional group, with diverse applications being reported. Sulfonyl fluorides are used as electrophilic warheads by both medicinal chemists and chemical biologists. The balance of reactivity and stability that is so attractive for these applications, particularly the resistance of sulfonyl fluorides to hydrolysis under physiological conditions, has provided opportunities for synthetic chemists. New synthetic approaches that start with sulfur-containing substrates include the activation of sulfonamides using pyrilium salts, the deoxygenation of sulfonic acids, and the electrochemical oxidation of thiols. Employing non-sulfur-containing substrates has led to the development of transition-metal-catalysed processes based on palladium, copper and nickel, as well as the use of SO₂F₂ gas as an electrophilic hub. Selectively manipulating molecules that already contain a sulfonyl fluoride group has also proved to be a popular tactic, with metal-catalysed processes again at the fore. Finally, coaxing sulfonyl fluorides to engage with nucleophiles, when required, and under suitable reaction conditions, has led to new activation methods. This Review provides an overview of the challenges in the efficient synthesis and manipulation of these intriguing functional groups.

硫磺（vi)-氟化物交换 (SuFEx) 过程作为具有点击反应性的转化，激发了对具有硫氟键的亲电子物质的研究。其中，磺酰氟已成为主力官能团，据报道有多种应用。磺酰氟被药物化学家和化学生物学家用作亲电子弹头。对这些应用非常有吸引力的反应性和稳定性的平衡，特别是磺酰氟在生理条件下对水解的抵抗力，为合成化学家提供了机会。从含硫底物开始的新合成方法包括使用吡啶盐活化磺胺类药物、磺酸脱氧和硫醇的电化学氧化。₂ F ₂气体作为亲电子枢纽。选择性地操纵已经含有磺酰氟基团的分子也被证明是一种流行的策略，金属催化过程再次成为主流。最后，在需要时并在合适的反应条件下，诱导磺酰氟与亲核试剂结合，导致了新的活化方法。本综述概述了有效合成和操作这些有趣的官能团所面临的挑战。