The chromone "altechromone A" was synthesized as a substructure in the course of natural product synthesis. Its architecture was verified by X-ray analysis, but spectroscopic data showed a strong deviation from the reported data. By comparison with the synthesized isomers the structure of altechromone A was revised.

An efficient and straightforward, one‐pot sequence gives access to highly functionalized 3‐cinnamoyl‐2‐styrylchromones in excellent yields. The low solubility of the target molecules allows convenient isolation. The formation of an α,α‐dicinnamoylated acetophenone, as a consequence of a two‐fold Baker–Venkataraman sequence, has to be anticipated.

A variety of 2-acyl-, 2-aroyl-and 2-formyl-substituted phenols are converted in a one-pot reaction with α,β-unsaturated carboxylic acid chlorides into the corresponding 3-alkenylcoumarins. Especially the labile 3-vinylcoumarins are readily available by the simple to perform protocol. If longer alkenyl chains are involved in position 3, small molecules with excel-

Direct anodic oxidation of 2,4-dimethylphenol yields an unusual spiropentacyclic scaffold. An intermediate was isolated and structurally elucidated which strongly supports the postulated mechanism for the stereoselective formation of this spirolactone moiety. Additionally, we report an ameliorated protocol for the rearrangement to the spirolactone system.