Periselectivity in the Aza-Diels–Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study

Marc Presset (1) , Michel Rajzmann (1) , Guillaume Dauvergne (1) , Jean Rodriguez (1) , Yoann Coquerel (1)

1 ISM2 - Institut des Sciences Moléculaires de Marseille

Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between ↵-oxoketenes generated by a thermally-induced Wol↵ rearrangement and 1-azadienes were observed experimentally as a function of the ↵-oxoketene and the 1-azadiene, as well as the reaction temperature and time. Some unexpected inversion in the diastereoselectivity was observed, too. These variations in selectivities were fully rationalized by computational modeling using density functional theory (DFT) methods.

Mots clés: hetero-Diels-Alder; ketenes; imines; periselectivity; density functional theory; hetero-Diels-Alder

Domaines: Chimie organique

Marc Presset, Michel Rajzmann, Guillaume Dauvergne, Jean Rodriguez, Yoann Coquerel. Periselectivity in the Aza-Diels–Alder Reaction of 1-Azadienes with α-Oxoketenes: A Combined Experimental and Theoretical Study. Molecules, 2020, 25 (20), pp.4811. ⟨10.3390/molecules25204811⟩. ⟨hal-02990656⟩