from first principles PP-I-1

OP-II-5Mechanisms of Catalytic Reactions of NorbornadieneFlid V.R., Evstigneeva E.M., Shamsiev R.S.Lomonosov Moscow University of Fine Chemical Technologies, Moscow, Russiaeme2003@list.ruCatalytic processes with participation of norbornadiene (NBD) offer unique opportunity forsynthesis of broad range of polycyclic hydrocarbons. Effective usage of such syntheticmethods as homodimerization, codimerization and nonconventional allylation of NBN andNBD derivatives allows developing a unique strategy of preparation of carbocyclic structurescontaining methylene, vinyl and methylenecyclobutane functionalities.+OAccat.++++Problems of selectivity in multi-reaction pathways for NBN, NBD and their derivatives are ofgreat importance. Both rate and selectivity of NBD and NBN reactions with allyl esters can becontrolled. Mechanism of formation of nickel and palladium catalysts as well was extensivelystudied by a number of spectral and kinetic methods, key intermediates were identified, andconsistent mechanisms were proposed. Moreover, reaction pathways of NBD have beensimulated in the frame of DFT method. Factors influencing on selectivity have been revealed,what allowed synthesizing individual stereoisomers quantitatively. Both selectivity and TONdepend on composition of catalytic system and effective charge on the metal. A raw of newunsaturated compounds having double bonds of different reactivity is of interest for derivedrubber production.Comparative study of effectiveness of the usage of heterogeneous and homogeneousorganometallic catalysts was pursued. Common features and differences in the reactionmechanisms have been revealed.This work was financially supported by RFBR (# 11-03-00662-а).40