Radical ion probes. 11. reaction of 1,1-dimethyl-5,7-di-t- butylspiro[2.5]octa-4,7-dien-6-one with 5-hexenyl magnesium bromide

Article abstract of DOI:10.1016/S0040-4039(98)01975-3

In an ongoing effort to establish 1,1-dimethyl-5-7-di-t- butyspiro[2.5]octa-4,7-dien-6-one (1) as a mechanistic probe for the detection of single electron transfer (SET), the reaction of 1 with 5- hexenyl magnesium bromide was examined in the hopes of observing cyclization of any intermediate 5-hexenyl radicals to cyclopentylcarbinyl radicals. A polar process dominated the reaction, but in the less prevalent SET process, the 5-hexenyl → cyclopentylcarbinyl rearrangement was extensive, indicative of freely diffusing paramagnetic intermediates.