Jg. Gillmore et Jm. Tanko, 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, Tetrahedron letters, 39(48), 1998, pp. 8795-8798
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
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