84695-75-0Relevant academic research and scientific papers
Alkoxides as Nucleophiles in (?-Allyl)palladium Chemistry. Synthetic and Mechanistic Studies
Stanton, Susan A.,Felman, Steven W.,Parkhurst, Carol S.,Godleski, Stephen A.
, p. 1964 - 1969 (2007/10/02)
A new methodology for the use of alkoxides as nucleophiles in (?-allyl)palladium chemistry has been developed.In this process an allylic alcohol serves as the precursor to the ?-allyl complex and a triethylsilyl (TES) ether as precursor to the alkoxide nucleophile.By using Pd(PPh3)4 in CCl4, PPh3Cl+CCl3- is generated transposing the ROH into an oxyphosphonium group, R-O-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.
