10.1021/acs.orglett.9b02032.s001 Albert Artigas Albert Artigas Jordi Vila Jordi Vila Agustí Lledó Agustí Lledó Miquel Solà Miquel Solà Anna Pla-Quintana Anna Pla-Quintana Anna Roglans Anna Roglans A Rh-Catalyzed Cycloisomerization/Diels–Alder Cascade Reaction of 1,5-Bisallenes for the Synthesis of Polycyclic Heterocycles American Chemical Society 2019 polycyclic derivatives Polycyclic Heterocycles intramolecular Rh-catalyzed cycloisomerization alkene Cycloisomerization reactive cycloheptadiene Rh-Catalyzed cycloaddition variety bisallenes 1 polycyclic dihydroazepine rhodium Synthesi DFT calculations catalysi Cascade regioselective transformation novel methodology entry Bisallene dihydrooxepine derivatives 2019-07-11 19:47:44 Journal contribution https://acs.figshare.com/articles/journal_contribution/A_Rh-Catalyzed_Cycloisomerization_Diels_Alder_Cascade_Reaction_of_1_5-Bisallenes_for_the_Synthesis_of_Polycyclic_Heterocycles/8862233 A novel methodology to transform bisallenes into a variety of polycyclic derivatives employing rhodium­(I) catalysis has been developed. This transformation encompasses an intramolecular Rh-catalyzed cycloisomerization of bisallenes <b>1</b> to deliver a reactive cycloheptadiene, which concomitantly undergoes a regioselective [4 + 2] cycloaddition with alkenes. A complete mechanistic study of this transformation has been undertaken including DFT calculations. Overall, the methodology presented here constitutes a new and straightforward entry to polycyclic dihydroazepine and dihydrooxepine derivatives employing catalytic methods.