Jm. Tanko et al., CHARACTERIZATION OF A HYPERSENSITIVE PROBE FOR SINGLE-ELECTRON TRANSFER TO CARBONYL-COMPOUNDS, Perkin transactions. 2, (7), 1994, pp. 1407-1409
The radical anion generated from 1,1 hyl-5,7-di-tert-butylspiro[2.5]oc
ta-4,7-dien-6-one (1) undergoes facile ring opening yielding both the
3-degrees and 1-degrees distonic radical ions in a ratio of 9: 1 with
a rate constant greater-than-or-equal-to 10(7) s-1 (relief of cyclopro
pane ring strain and the generation of an aromatic ring provide the th
ermodynamic driving force for this rearrangement), the facility of C-C
bond cleavage in this radical anion and the observed electrochemistry
are reminiscent of the reductive cleavage of carbon-halogen bonds in
alkyl and benzylic halides: on the basis of these results, 1 emerges a
s a viable substrate for use as a hypersensitive SET probe in mechanis
tic studies.