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Rh‐catalyzed dynamic kinetic intramolecular [4+2] cycloaddition reaction of 1,3‐disubstituted allene‐1,3‐dienes afforded cis‐fused [4.3.0]bicyclic products with an excellent chemo‐, diastereo‐, and enantio‐selectivity. Many synthetically useful functional groups are tolerated. The synthetic utility has been demonstrated. Based on the careful experimental studies, a mechanism involving the rapid racemization...
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