<jats:title>Abstract</jats:title>
<jats:p>Controlled chemical construction is a characteristic feature of enzymes in the synthesis of structurally complicated natural products. One of the most representative examples of such a construction is dimerization for the synthesis of fungal dimeric anhydrides (FDAs). The initial biosynthetic proposal for the synthesis of FDAs was reported in 1965. Subsequently, nearly half a century later, unified biogenesis for the synthesis of structurally diverse FDAs was proposed through the identification and mechanistic analysis of the dimerization enzyme. This review presents an overview of the dimerization mechanism and discusses the structural diversification strategy of nature.</jats:p>
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