Stereo- and Regioselectivity in Palladium-Catalyzed Allylic Etherification

Stereoselective Synthesis of Cyclic Ethers via the Palladium-Catalyzed Intramolecular Addition of Alcohols to Phosphono Allylic Carbonates

“…However, the attempted addition of methanol to the alkyl substituted allylic carbonate ( 10 ) resulted in a crude mixture contianing the dienes ( 11 ) as the major products. Not suprisingly,18 p -methoxyphenol reacted with the alkyl substituted allylic carbonate ( 10 ) without incident.…”

Synthetic Uses of Phenols

“…π-Allylpalladium species generated by C−C bond cleavage of methylenecyclopropanes or by the C−C bond formation such as the Heck reaction also undergo phenoxylation 35,36 . Sinou and coworkers examined the regio-and stereochemistry of palladium catalyzed phenol O-allylation with allyl carbonates; acyclic primary allyl carbonates give primary phenyl ethers as the thermodynamic products; under kinetic control the selectivity was influenced by the steric and electronic nature of the allyl carbonates 37 . The phenoxylation of a 2-cyclohexenol carbonate proceeds with retention of configuration, which is consistent with the known π-allylpalladium chemistry (equation 7).…”

Palladium(II)-Catalyzed C–H Bond Activation/C–C Coupling/Intramolecular Tsuji–Trost Reaction Cascade: Facile Access to 2H-Pyranonaphthoquinones

“…The Pd(0) can catalyze the formation of the π-allylpalladium complex as a cationic species with inversion of configuration, leading to the formation of the alkoxide. 12 Meanwhile, the removal of the Boc protecting group would be conducted simultaneously in the presence of Pd(0), forming the intermediate H. Then, the nucleophile alkoxide attacked the backside of the coordinated π-allyl giving the target compound 1a and Pd(0) catalyst, which is reoxidized by 2 equiv of Cu(OAc) 2 to regenerate the Pd(II) catalyst to complete the catalytic cycle. The mechanism provided a rational explanation for the generation of compounds 8 and 9 in the control experiment (Scheme 4a).…”