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Ring-opening of Some Radicals containing the Cyclopropylmethyl System
Beckwith, Athelstan L. J.,Moad, Graeme
, p. 1473 - 1482 (2007/10/02)
Mono- and bi-cyclic radicals containing the cyclopropylmethyl system are readily generated by interaction of the appropriate halides with triphenyl- or tributyl-stannane.Each radical studied underwent ring-opening by fission of the more substituted βγ-bond.In the case of the secondary radical (12b) the new double bond was formed preferentially in the trans-configuration.Rate constants, which cannot be determined with high accuracy by this method, lie in the range 1E7-3E8 s-1 at 25 deg C.When generated by the flow method in the e.s.r. cavity α-hydroxycyclopropylmethyl radicals undergo β-fission followed by 1,5-hydrogen atom t ransfer to afford enoxyl radicals.The latter reaction occurs more slowly in water than in non-polar solvents.The rigid hydroxynortricyclyl (43) undergoes preferential fission of the less substituted βγ-bond, possibly because of the dipolar nature of the transition state.
