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Ring expansion of a catenane without destruction of the interlocked structu
re was attained by Diels-Alder reaction followed by ozonolysis. Annulation
by Diels-Alder reaction introduced a C4 fragment onto the ring, and the ozo
nolysis scissored the resulting double bond to expand the catenane ring. Th
e annulation-ring scission sequence provides a general approach for changin
g the connectivity on a catenane ring without destroying the interlocked st
ructure.