Premium
Palladium(II)‐Catalyzed Allylic CH Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation
Author(s) -
Xing Xiangyou,
O'Connor Nicholas R.,
Stoltz Brian M.
Publication year - 2015
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201504007
Subject(s) - allylic rearrangement , palladium , selectivity , catalysis , chemistry , steric effects , combinatorial chemistry , photochemistry , organic chemistry
The use of Oxone and a palladium(II) catalyst enables the efficient allylic CH oxidation of sterically hindered α‐quaternary lactams which are unreactive under known conditions for similar transformations. This simple, safe, and effective system for CH activation allows for unusual tunable selectivity between a two‐electron oxidation to the allylic acetates and a four‐electron oxidation to the corresponding enals, with the dominant product depending on the presence or absence of water. The versatile synthetic utility of both the allylic acetate and enal products accessible through this methodology is also demonstrated.