RADICAL-ION PROBES - 11 - REACTION OF METHYL-5,7-DI-T-BUTYLSPIRO[2.5]OCTA-4,7-DIEN-6-ONE WITH 5-HEXENYL MAGNESIUM BROMIDE

In an ongoing effort to establish 1,1-dimethyl-5,7-di-t-butylspiro[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 magne sium bromide was examined in the hopes of observing cyclization of any intermediate 5-hexenyl radicals to cyclopentylcarbinyl radicals. A po lar process dominated the reaction, but in the less prevalent SET proc ess, the 5-hexenyl --> cyclopentylcarbinyl rearrangement was extensive , indicative of freely diffusing paramagnetic intermediates. (C) 1998 Elsevier Science Ltd. All rights reserved.