title: Conversion of Allylic Alcohols into Allylic Nitromethyl Compounds via a Palladium-Catalyzed Solvolysis: An Enantioselective Synthesis of an Advanced Carbocyclic Nucleoside Precursor(1).
abstract: 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 CH(3)NO(2) 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 pi-allylpalladium complexes. This methodology serves as a centerpiece for the synthesis of an important carbocyclic nucleoside intermediate.
authors.affiliation: Department of Chemistry, Occidental College, Los Angeles, California 90041.
authors.forename: Donald R.
authors.initials: DR
authors.lastname: Deardorff
authors.forename: Kenneth A.
authors.initials: KA
authors.lastname: Savin
authors.forename: Craig J.
authors.initials: CJ
authors.lastname: Justman
authors.forename: Zarir E.
authors.initials: ZE
authors.lastname: Karanjawala
authors.forename: James E.
authors.initials: JE
authors.lastname: Sheppeck II
authors.forename: David C.
authors.initials: DC
authors.lastname: Hager
authors.forename: Nebil
authors.initials: N
authors.lastname: Aydin