In an attempt to trap any radical intermediates with a sufficiently long lifetime, we performed the radical alkene transfer reaction in the presence of 2,2,6,6tetramethypipieridine 1-oxyl (TEMPO) as a radical trap. However, no adducts between TEMPO and radical intermediates could be observed. We next set out to investigate the importance of the silicon atom for the radical reaction. We subjected the allylic ether 9, which can be considered an all-carbon analogue of the substrates, to the alkene transfer reaction conditions (Scheme 4a). Interestingly, this resulted in the formation of a 4:1 mixture of halogenated and reduced cyclic products 10 and 11, respectively. This suggests that the silicon atom plays a key role in facilitating the ring opening of a cyclic radical intermediate. Next, we performed the reaction in the absence of methanol (Scheme 4b). Under these conditions, the only observed product was a disiloxane-bridged dimer 12a, which suggests that the reaction goes through a silylium ion. Silylium ions are known to be extremely reactive towards nucleophiles, and even traces of water are known to result in disiloxane formation. Under the normal reaction conditions, however, the silylium ion is captured by methanol to produce methyl silyl ether 5 as the only product.