Here we present an unprecedented chemoselective hydroboration for aldehydes and ketones catalysed by actinides. The reaction features a very low catalyst loading (0.1-0.004 mol%) and quantitative product formation in less than 15 minutes, at room temperature. Thermodynamic and kinetic studies including stoichiometric and labeling studies with deuterated pinacolborane allow us to propose a plausible mechanism for this remarkable catalytic regeneration of a Th-H bond via carbonyl hydroboration.

The challenging hydroboration of esters is achieved using simple uranium and thorium amides, U­[N­(SiMe3)2]3 and [(Me3Si)2N]2An­[κ2-(N,C)-CH2Si­(CH3)2N­(SiMe3)] (An = Th or U) acting as precatalysts in the reaction with pinacolborane (HBpin). All three complexes showed impressive catalytic activities, reaching excellent yields. A large scope of esters was investigated including aliphatic, aromatic, and heterocyclic esters that were transformed cleanly to the corresponding hydroborated alcohols, which readily hydrolyzed to the free alcohols. Moreover, the actinide catalysts demonstrated unexpected high functional tolerance toward nitro, halide, cyano, and heteroaromatic functional groups. The reaction exhibited excellent selectivity toward the ester when additional double and triple unsaturated C–C bonds were present. Lactones and poly caprolactone have been successfully cleaved to the monomeric units, showing a great promise toward polymer degradation and recycling. Detailed kinetic studies are provided in order to determine the rate dependence on the concentration of catalyst, HBpin, and ester. A plausible mechanism is proposed based on stoichiometric reactions, DFT calculations, thermodynamic measurements, and deuterium-labeling studies.

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A new class of actinide complexes [(L)­An­(N­{SiMe3}2)3] (An = Th or U) (Th1–Th3 and U1–U3) supported by highly nucleophilic seven-membered N-heterocyclic iminato ligands were synthesized and fully characterized by single-crystal X-ray diffraction. These complexes were successfully exploited as powerful catalysts for the addition of alcohols to carbodiimides to yield the corresponding desirable isourea products at room temperature with short reaction times and excellent yields. Thorough stoichiometric, thermodynamic, and kinetic studies were carried out, allowing us to propose a plausible mechanism for the catalytic reaction.

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