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A remarkable proline‐catalyzed method for the construction of biologically interesting oxygen‐bridged tricyclic ketal skeletons was uncovered by starting from a variety of readily available cyclic 1,3‐diketones and either 1,4‐ or 1,5‐dicarbonyl substrates. The approach, which mimics a biosynthetic Knoevenagel condensation/[4+2] cycloaddition sequence, establishes a viable synthetic strategy for the...
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