TY - JOUR
T1 - The mechanism of the β-acyloxyalkyl radical rearrangement
T2 - Kinetic and 18O-labelling studies
AU - Beckwith, Athelstan L.J.
AU - Duggan, Peter J.
PY - 1992
Y1 - 1992
N2 - Experiments with 18O-enriched substrates indicate that the rearrangement of 2-butanoyloxy-2,2-dimethyl radical 1 (R = Pr) by migration of the acyloxy group involves complete transposition of the ether and carbonyl oxygen atoms, whereas the similar but much faster rearrangement of the substituted cholestanyl radical 11 proceeds with only 24% transposition. The rearrangement of 1 is considered to involve a five-membered cyclic transition state 2, while that of 11 probably proceeds via a tight anion-radical-cation pair 21.
AB - Experiments with 18O-enriched substrates indicate that the rearrangement of 2-butanoyloxy-2,2-dimethyl radical 1 (R = Pr) by migration of the acyloxy group involves complete transposition of the ether and carbonyl oxygen atoms, whereas the similar but much faster rearrangement of the substituted cholestanyl radical 11 proceeds with only 24% transposition. The rearrangement of 1 is considered to involve a five-membered cyclic transition state 2, while that of 11 probably proceeds via a tight anion-radical-cation pair 21.
UR - http://www.scopus.com/inward/record.url?scp=37049072581&partnerID=8YFLogxK
U2 - 10.1039/p29920001777
DO - 10.1039/p29920001777
M3 - Article
AN - SCOPUS:37049072581
SN - 1472-779X
SP - 1777
EP - 1783
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 10
ER -