Mechanism and transition-state structure of hydride-transfer reactions mediated by nad(p)h-models
1986
Abstract The energy to transfer one electron from NAD(P)H and related 1,4-dihydropyridines to a series of substrates is calculated and compared with the experimental activation energy for transfer of a hydride equivalent between these species. It is concluded that single electron-transfer (SET) cannot occur as a primary step in the overall hydride-transfer process except for substrates with very strong one-electron oxidizing properties. A simple valence-bond configuration mixing (VBCM) model is presented, that rationalizes the general occurrence of concerted hydride transfer as the lowest energy reaction-pathway and furthermore explains why the activation energy of such a concerted pathway is often linearly related to that of a -hypothetical- SET process. For one intramolecular and two related, intermolecular hydride-transfer reactions the temperature dependence of the primary kinetic isotope effect (TDKIE) was studied. For the intramolecular reaction, where a face to face orientation of the reactants is enforced, the TDKIE parameters suggest the occurrence of a bent hydride-transfer pathway. For both intermolecular reactions, however, a linear transition-state geometry is indicated. MNDO calculations of the reaction profile for hydride transfer from a 1,4-dihydropyridine to either a positively charged substrate (i.e. the pyridinium-ion) or to a neutral substrate (i.e. 1,1-dicyanoethylene) confirm, that a linear transition-state geometry is favoured, unless the system is geometrically restrained to prevent such a geometry. The MNDO calculations furthermore indicate that in a linear transition-state almost unimpeded rotation can occur about the C...H...C axis. This rotation interconverts the relative orientation of the reactants between parallel-exo and tilted-endo, which may have important consequences for the interpretation of the stereochemical outcome of reactions involving (pro) chiral reactants.
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