Abstract
Main observation and conclusionThe first example of Rh‐catalyzed kinetic resolution of 1,3‐disubstituted allene‐1,3‐dienes involving intramolecular [4+2]‐cycloaddition has been developed. Followed by C=C isomerization, the reaction finally afforded aza‐[4.3.0]bicyclic compounds with a very high enantio‐ and E‐selectivity. The mechanism has been unveiled by careful control experiments. The synthetic potentials of highly enantioenriched bicyclic products have also been demonstrated.
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