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

ABSTRACT: Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between ?-oxoketenes generated by a thermally-induced Wolff 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.

SUBMITTER: Presset M

PROVIDER: S-EPMC7587935 | biostudies-literature | 2020 Oct

REPOSITORIES: biostudies-literature

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

Presset Marc M Rajzmann Michel M Dauvergne Guillaume G Rodriguez Jean J Coquerel Yoann Y

Molecules (Basel, Switzerland) 20201020 20

Inversions in the periselectivity of formal aza-Diels-Alder cycloadditions between α-oxoketenes generated by a thermally-induced Wolff rearrangement and 1-azadienes were observed experimentally as a function of the α-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. ...[more]

PMID: 33092017

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