Ladder-shaped tetracyclic and heptacyclic ethers containing a 6/7 cis-fused ring system have been synthesized. The synthesis features convergent coupling of monocyclic building blocks through esterification, ring-closing reaction using a low-valent titanium complex, and hydroxy dithioacetal cyclization. The double reaction strategy enabled expeditious synthesis of the heptacyclic ether in only thirteen steps from the building blocks.
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