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We report the unexpected discovery of three fully unprecedented, sulfonyl\u2010bridged alkaloid dimers (sulfadixiamycins A\u2013C) from recombinant <jats:italic>Streptomyces<\/jats:italic> species harboring the entire xiamycin biosynthesis gene cluster. Sulfadixiamycins exhibit moderate antimycobacterial activities and potent antibiotic activities even against multidrug\u2010resistant bacteria. Gene inactivation, complementation, and biotransformation experiments revealed that a flavin\u2010dependent enzyme (XiaH) plays a key role in sulfadixiamycin biosynthesis. XiaH mediates a radical\u2010based, three\u2010component reaction involving two equivalents of xiamycin and sulfur dioxide, which is reminiscent of radical styrene\/SO<jats:sub>2<\/jats:sub> copolymerization.<\/jats:p>","DOI":"10.1002\/anie.201506541","type":"journal-article","created":{"date-parts":[[2015,9,14]],"date-time":"2015-09-14T19:40:54Z","timestamp":1442259654000},"page":"13279-13283","source":"Crossref","is-referenced-by-count":64,"title":["Bacterial Synthesis of Unusual Sulfonamide and Sulfone Antibiotics by Flavoenzyme\u2010Mediated Sulfur Dioxide 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