AbstractAs part of a study aimed at generating analogues of hyperforin (1), the reaction of this prenylated phloroglucinol with various hydride reducing agents was investigated. Hyperforin contains two β‐dicarbonyl systems, one of which is non‐enolizable, and it was interesting to assess the relative reactivity of these structural elements in the highly compact framework of the natural product. Depending on the reducing agent employed, a surprising range of compounds could be obtained, sometimes in synthetically useful yields. The stereochemistry of the LiAlH4‐reduced product was secured by X‐ray analysis and served as a base for elucidating the configuration of a series of reduced and deoxygenated analogues obtained with other reducing agents. The chemoselectivity observed in these reactions is apparently the result of a combination of metal‐chelation and hydrogen‐bonding effects. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)