158478-10-5Relevant academic research and scientific papers
The Palladium-Catalyzed Cross-Coupling Reaction of Organosilicon Compounds with Allylic Carbonates or Diene Monoxides
Matsuhashi, Hayao,Asai, Satoshi,Hirabayashi, Kazunori,Hatanaka, Yasuo,Mori, Atsunori,Hiyama, Tamejiro
, p. 1943 - 1952 (1997)
The cross-coupling reaction of allylic carbonates with organosilanes was found to proceed without fluoride ion activation under mild conditions by using a coordinatively unsaturated palladium complex as a catalyst.The reaction was assumed to proceed through an allylpalladium alkoxide derived from the allylic carbonate substrate and a palladium(0) species, the alkoxo ligand activating the organosilicon reagent.Likewise, diene monoxides also underwent cross-coupling with alkenyl- and arylfluorosilanes in moderate to high yields.
Conversion of allylic alcohols into allylic nitromethyl compounds via a palladium-catalyzed solvolysis: An enantioselective synthesis of an advanced carbocyclic nucleoside precursor
Deardorff, Donald R.,Savin, Kenneth A.,Justman, Craig J.,Karanjawala, Zarir E.,Sheppeck II, James E.,Hager, David C.,Aydin, Nebil
, p. 3616 - 3622 (2007/10/03)
A two-step reaction sequence to homoallylic nitro compounds from allylic alcohols is presented. Ethoxy carbonylation of the alcohols with ethyl chloroformate provides the corresponding allylic ethyl carbonates in high yields. Exposure of these substrates to catalytic palladium(0) in CH3NO2 initiates a reaction sequence, ionization-decarboxylation-nitromethylation, that culminates with the formation of nitroalkenes. The regio- and stereochemical outcomes of the nitromethyl allylation reaction can be explained by the behavior of the transient π-allylpalladium complexes. This methodology serves as a centerpiece for the synthesis of an important carbocyclic nucleoside intermediate.
