Russian Chemical Bulletin

, Volume 56, Issue 2, pp 320–324 | Cite as

Catalytic hydroallylation of norbornadiene with allyl formate

  • I. P. Stolyarov
  • A. E. Gekhman
  • I. I. Moiseev
  • A. Yu. Kolesnikov
  • E. M. Evstigneeva
  • V. R. Flid


Norbornadiene (NBD) reacts with allyl esters All—OC(O)R (R = Me, But, Ph, CCl3, CF3) in acetonitrile solutions of palladium(0) complexes to give a mixture of four isomeric nontraditional allylation products and the corresponding carboxylic acids. Under similar conditions, the reaction of NBD with allyl formate in solutions of Pd0 and PdII complexes occurs selectively, resulting in the product of addition of the allyl fragment and the H atom to an NBD double bond, 5-allylbicyclo[2.2.1]hept-2-ene, and CO2. The hydroallylation of NBD is accompanied by catalytic addition of formic and acetic acids to one double bond of the diene to give bicyclo[2.2.1]hept-2-en-5-ol and nortricyclan-3-ol acetates and formates. Unlike most known palladium-based catalyst systems, these complexes exhibit catalytic activity also in the absence of phosphines.

Key words

norbornadiene allylation catalytic hydroallylation palladium(0) complexes palladium(II) complexes allyl esters 


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Copyright information

© Springer Science+Business Media, Inc. 2007

Authors and Affiliations

  • I. P. Stolyarov
    • 1
  • A. E. Gekhman
    • 1
  • I. I. Moiseev
    • 1
  • A. Yu. Kolesnikov
    • 2
  • E. M. Evstigneeva
    • 2
  • V. R. Flid
    • 2
  1. 1.N. S. Kurnakov Institute of General and Inorganic ChemistryRussian Academy of SciencesMoscowRussian Federation
  2. 2.M. V. Lomonosov Moscow State Academy of Fine Chemical TechnologyMoscowRussian Federation

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