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Hydrative Aminoxylation of Ynamides: One Reaction, Two Mechanisms.

ABSTRACT: Organic synthesis boasts a wide array of reactions involving either radical species or ionic intermediates. The combination of radical and polar species, however, has not been explored to a comparable extent. Herein we present the hydrative aminoxylation of ynamides, a reaction which can proceed by either a polar-radical crossover mechanism or through a rare cationic activation. Common to both processes is the versatility of the persistent radical TEMPO and its oxidised oxoammonium derivative TEMPO+ . The unique mechanisms of these processes are elucidated experimentally and by in-depth DFT-calculations.

SUBMITTER: Pinto A

PROVIDER: S-EPMC5838720 | biostudies-other | 2018 Feb

REPOSITORIES: biostudies-other

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Hydrative Aminoxylation of Ynamides: One Reaction, Two Mechanisms.

Pinto Alexandre A Kaiser Daniel D Maryasin Boris B Di Mauro Giovanni G González Leticia L Maulide Nuno N

Chemistry (Weinheim an der Bergstrasse, Germany) 20180124 10

Organic synthesis boasts a wide array of reactions involving either radical species or ionic intermediates. The combination of radical and polar species, however, has not been explored to a comparable extent. Herein we present the hydrative aminoxylation of ynamides, a reaction which can proceed by either a polar-radical crossover mechanism or through a rare cationic activation. Common to both processes is the versatility of the persistent radical TEMPO and its oxidised oxoammonium derivative TE ...[more]

PMID: 29293283

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