Diimide reductions result in the syn addition of dihydrogen to alkenes and alkynes. This observation has led to the proposal that the mechanism involves concerted hydrogen transfer from cis-diimide to the substrate. The cis isomer is the less stable of the two; however, acid catalysis may speed up equilibration of the trans and cis isomers.
Diimide is typically generated either through the oxidation of hydrazine or the decarboxylation of potassium azodicarboxylate. Kinetic experiments suggest that regardless of its method of generation, the formation of diimide is rate-limiting. The transition state of the hydrogen transfer step is likely early; however, high stereoselectivity has been obtained in many reductions of chiral alkenes.
The order of reactivity of unsaturated substrates is: alkynes, allenes > terminal or strained alkenes > substituted alkenes. Trans alkenes react more rapidly than cis alkenes in general. The reactivity difference between alkynes and alkenes is usually not great enough to isolate intermediate alkenes; however, alkenes can be isolated from allene reductions.
Diimide reduces symmetrical double bonds i.e.,C=C. N=N, O=O etc. unsymmetrical double bonds can not be reduced