Journal of the American Chemical Society, Vol.130, No.37, 12256-12256, 2008
Alkali metal reductions of organic molecules: Why mediated electron transfer from lithium is faster than direct reduction
Lithium metal reductions are widely employed in organic synthesis, where it is common to employ a "mediator" to speed up the electron transfer kinetics. We present experimental data for the electrode kinetics of the reduction of the most common mediator, 4,4'-di-tert-butyl-1,1'-biphenyl (DBB) in tetrahydrofuran (THF) over a range of temperatures. Using corresponding data for the oxidation of lithium we present quantitative estimates of the kinetic advantage for the use of DBB as a mediator in lithium reductions, over, in particular, direct reduction using lithium metal.