A new methodology for the use of alkoxides as nucleophiles in (ir-allyl)palladium chemistry has been developed. In this process an allylic alcohol serves as the precursor to the ir-allyl complex and a triethylsilyl (TES) ether as precursor to the alkoxide nucleophile. By using Pd(PPh3)4 in CC14, PPh3Cl+CCl3" is generated transposing the ROH into an oxyphosphonium group, R-0-P+Ph3, and liberating Cl". The Cl deprotects the TES ether, providing the nucleophile in situ. Application of this reaction to the preparation of a variety of furans is discussed. This process was determined to proceed with overall predominant retention of configuration. Mechanistic studies suggest a small energy difference between attack by alkoxide on the allyl ligand of the intermediate complex and attack on the metal, followed by reductive elimination.

Die Cyclisierung der Verbindungen mit Allylalkoholgruppierung (III) [bzw. (IV)], (IX) und (XIV) zu den Tetrahydrofuran‐Spiroverbindungen (V), (X) bzw. (XV)/(XVI) durch Vermittlung der Pd(0)‐Komplexe Pd(DIPHOS)2 und Pd(PPh3)4 wird untersucht.