The use of ring opening rearrangement of cyclopropylmethyl radicals to
but-3-enyl radicals as radical clocks and as probes of reaction mecha
nism is discussed relation to a variety of both enzyme-catalysed and c
hemical reactions. Similar studies using heterocyclic analogues, e.g.
oxiranylmethyl radicals, are also reported. Factors which influence bo
th the rate and regioselectivity of ring opening of cyclopropylmethyl
and related radicals have been analysed. The use of this rearrangement
in synthetic methodology has also been surveyed.