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Bisacetal-containing bicyclic isoxazolidine derivatives bearing four constant stereocenters were formed with exemplary stereoselectivities. A plausible effect pathway had been recommended according to 18O-labeling control experiments.A facile approach to the completely substituted cyclopentenones concerning an unprecedented benzofuran-ring-opening is explained. The cleavage of a benzofuran endocyclic C2-O bond proceeded smoothly in the lack of any transition material catalyst