The Dimerization of Precocene I

In an earlier work we reported that treatment of precocene I with Brönsted and Lewis acids produces its oligomerization, giving dimers, trimers, tetramers, etc. Now, in this article we show that bromination of precocene I with phenyltrimethylammonium tribromide (PTT) blocks its oligomerization giving a dibromo- dimer, which was reduced with tri-n-butyl tin hydride affording the same dimer obtained in the reactions with acid, thus avoiding the oligomerization. Additionally, the oxidations of precocene I with Jones reagent afforded the corresponding 3-hydroxy-4-chromanone, 3,4-chromandione, 3,4-diacid, and two dimers.