Abstract
Ring-opening oligomerization of the two stereoisomers of a bicyclic lactone 4-bromo-6,8-dioxabicyclo[3.2.1]octan-7-one was investigated in dichloromethane and chloroform at −40 and 0°C using antimony pentachloride, phosphorus pentafluoride, and trifluoromethanesulfonic acid as initiators. The axial isomer (5a) showed a tendency to cyclodimerize, particularly at higher temperature, whereas the equatorial isomer (5e) was much less reactive and it afforded only a small amount of cyclic oligomers. Reductive debromination using tri-n-butylstannane converted the cyclic dimer (6) of 5a to the cyclic dimer (2) of 6,8-dioxabicyclo[3.2.1]octan-7-one (1), indicating that 6 was composed of a pair of the enantiomeric monomeric units. The specific formation of the cyclic dimer 6 from the axial isomer 5a was interpreted in terms of the participation of bromonium ions in the propagation.
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Okada, M., Sumitomo, H., Ito, K. et al. Cationic Ring-Opening Oligomerization of the Two Stereoisomers of 4-Bromo-6,8-dioxabicyclo[3.2.1]octan-7-one. Polym J 20, 55–63 (1988). https://doi.org/10.1295/polymj.20.55
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DOI: https://doi.org/10.1295/polymj.20.55