A unified synthesis of diverse pentafluorobenzenesulfonamide reactive fragments was developed which was based on the reaction between diverse, readily-available substrates and rhodium nitrenoid intermediates formed from pentafluorobenzenesulfonamide. The approach enabled the synthesis of 21 reactive fragments whose diversity stemmed from both that of the substrates, and the rich chemistry of rhodium nitrenoids. Five of the reactive fragments were profiled against HeLa cell lysate, which demonstrated that the constellation of modified proteins was critically dependent on the specific reactive fragment used.