Abstract
Abstract The mechanism of reduction reactions by 1,4-dihydronicotinamides is investigated from the theoretical point of view of the electron configuration and orbital interactions for many systems. The following conclusions are drawn: (1) The reactions are situated near the one-electron-transfer region in the mechanistic spectra dependent on the donor-acceptor property of the reactants; (2) the hydride-equivalent transfers involved, whether concerted or not, proceed more or less in accordance with the nature of the sequential electron-proton-electron shift rather than via direct hydride-ion transfer; (3) the paradoxical frontier orbital interaction between the σ-LUMO of C4-H of 1,4-dihydronicotinamides and the LUMO of substrates is significantly involved in the transfer of the protonic entity. Pseudoexcitation is classified into Type I, where the normal HOMO-LUMO interaction remains important in addition to the LUMO-LUMO and HOMO-HOMO interactions, and Type II, where the HOMO-LUMO interaction contributes little. The NAD(P)H reduction reactions are predicted to belong to Type II.
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