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Hydrative Aminoxylation of Ynamides: One Reaction, Two Mechanisms
Author(s) -
Pinto Alexandre,
Kaiser Daniel,
Maryasin Boris,
Di Mauro Giovanni,
González Leticia,
Maulide Nuno
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201706063
Subject(s) - cationic polymerization , polar , derivative (finance) , chemistry , ionic bonding , reaction mechanism , radical , crossover , mechanism (biology) , combinatorial chemistry , computational chemistry , photochemistry , polymer chemistry , organic chemistry , computer science , catalysis , ion , physics , financial economics , astronomy , artificial intelligence , economics , quantum mechanics
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.