Uranyl(VI) Triflate as Catalyst for the Meerwein–Ponndorf–Verley Reaction

Marie Kobylarski (1) , Louis Monsigny (1) , Pierre Thuéry (1) , Jean-Claude Berthet (1) , Thibault Cantat (1)

1 LCMCE - Laboratoire de Chimie Moléculaire et de Catalyse pour l'Energie (ex LCCEF)

Catalytic transformation of oxygenated compounds is challenging in f-element chemistry due to the high oxophilicity of the f-block metals. We report here the first Meerwein–Ponndorf–Verley (MPV) reduction of carbonyl substrates with uranium-based catalysts, in particular from a series of uranyl(VI) compounds where [UO2(OTf)2] (1) displays the greatest efficiency (OTf = trifluoromethanesulfonate). [UO2(OTf)2] reduces a series of aromatic and aliphatic aldehydes and ketones into their corresponding alcohols with moderate to excellent yields, using iPrOH as a solvent and a reductant. The reaction proceeds under mild conditions (80 °C) with an optimized catalytic charge of 2.3 mol % and KOiPr as a cocatalyst. The reduction of aldehydes (1–10 h) is faster than that of ketones (>15 h). NMR investigations clearly evidence the formation of hemiacetal intermediates with aldehydes, while they are not formed with ketones.

Domaines: Catalyse; Chimie de coordination

Marie Kobylarski, Louis Monsigny, Pierre Thuéry, Jean-Claude Berthet, Thibault Cantat. Uranyl(VI) Triflate as Catalyst for the Meerwein–Ponndorf–Verley Reaction. Inorganic Chemistry, In press, 60, pp.16140-16148. ⟨10.1021/acs.inorgchem.1c01798⟩. ⟨cea-03384490⟩