Palladium-catalyzed cyclization of 1,omega-dienols: multiple ways to intramolecularly trap a carbocation.
The tandem catalytic cyclization-rearrangement of 1,omega-dien-3-ols by palladium(II) produces different types of products, depending on the structure of starting material. The pinacol rearrangement, benzannulation, and oxy-Cope rearrangement are major pathways of transforming the putative sigma-alkylpalladium carbocation. Turnover of the cyclization is achieved by beta-hydride elimination and reoxidation of palladium with benzoquinone. The overall course of the reaction is very sensitive to small changes in the substrate structure.
Korotchenko
Vasily N
VN
Department of Chemistry, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina 27599-3290, USA.
Gagné
Michel R
MR
D002244:Carbon / Q000737:chemistry*; D002384:Catalysis; D003500:Cyclization; D003516:Cycloparaffins / Q000138:chemical synthesis* / Q000737:chemistry; D015394:Molecular Structure; D010165:Palladium / Q000737:chemistry*
D003516:Cycloparaffins; D010165:Palladium; D002244:Carbon