Details

Autor(en) / Beteiligte

• Xing, Xiangyou
• O'Connor, Nicholas R.
• Stoltz, Brian M.

Titel

Palladium(II)-Catalyzed Allylic CH Oxidation of Hindered Substrates Featuring Tunable Selectivity Over Extent of Oxidation

Ist Teil von

• Angewandte Chemie (International ed.), 2015-09, Vol.54 (38), p.11186-11190

Ort / Verlag

Weinheim: WILEY-VCH Verlag

Erscheinungsjahr

2015

Link zum Volltext

Quelle

Alma/SFX Local Collection

Beschreibungen/Notizen

• The use of Oxone and a palladium(II) catalyst enables the efficient allylic CH oxidation of sterically hindered α‐quaternary lactams which are unreactive under known conditions for similar transformations. This simple, safe, and effective system for CH 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. SwitcheR‐O‐O‐H: The use of potassium peroxymonosulfate (KOSO2‐O‐O‐H, Oxone) and a PdII catalyst enables the efficient allylic CH oxidation of sterically hindered α‐quaternary lactams. This simple and environmentally safe protocol allows 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.