Reduction of 2-bromo-1-phenylethylidenemalononitrile 1 with the chiral NAD (P) Hmodel (SS)-1-benzyl- 3-(p-tolylsulfinyl)-1, 4-dihydropyridine 2 gives the cyclopropane ring product (S)-2-phenylcyclopropane-1, 1-dicarbonitrile 3 with 54.5% enantiomeric purity.

The reaction of 1-benzyl-1,4-dihydronicotinamide with a series of 1,1-di-p-substituted-phenyl-2,2-dinitroethylenes in oxygen-saturated acetonitrile produced various amounts of the corresponding ethanes and diaryl ketones according to the electronic structure of the substituent groups indicating a spectrum of intermediate mechanism between polar mechanism and SET mechanism.

A series of compounds, o-bromomethylbenzylidene-malononitrile (1), dimethyl o-bromomethyl-benzylidenemalonate (2) and methyl ∞-cyano-o-bromomethylcinnamate (3) were reduced in the dark and under irradiation by an NAD(P)H model, 1-benzyl-1,4-dihydronicotinamide (BNAH). Two different mechanisms were found, i.e. one-step hydride transfer (polar pathway) and multi-step sequence initiated by single electron transfer (SET pathway). The effect of electron-withdrawing groups on the reactivity of the substrates were discussed in terms of Hammett substituent constants, 13C NMR chemical shift values and cyclic voltammetric redox potentials, and their correlations.

9-Fluorenylidenemalononitrile reacts with 10-methyl- 9,10-dihydroacridine in deaerated acetonitrile under irradiation with λ>320nm to give a coupling product 9-dicyanomethyl-9-(10A-methyl-9A-cridinyl)fluorene, characterized by X-ray crystallographic, MS and NMR analyses.

The reduction of 2 bromo-1 (p-X-phenylethylidenemahmonitrile (X-BPM: X=H, F, C1, Br, CN) by ADHmodels BNAH and AcrH2 has been investigated. Based on product analysis, kinetic isotope effect, and free energy relationship, a direct hydride transfer and an electron transfer hydrogen abstraction mechanism is proposed, respectively.