Catalyst-free depolymerization of polycaprolactone to silylated monoesters and iodide derivatives using iodosilanes.

The homogeneous depolymerization of polycaprolactone (PCL) with excess iodotrimethylsilane (Me3SiI) proceeds without catalysts and selectively afforded I(CH2)5CO2SiMe3 or a mixture of I(CH2)5CO2SiMe3 and I(CH2)5CO2I depending on the solvent (CH2Cl2, MeCN). The latter mixture can undergo methanolysis or hydrolysis into the valuable ester I(CH2)5CO2Me or the acid I(CH2)5CO2H. In contrast, SiH2I2 depolymerized PCL into the fully deoxygenated species I(CH2)6I and n-hexane.

Reductive depolymerization of polyesters and polycarbonates with hydroboranes by using a lanthanum(III) tris(amide) catalyst.

The homogeneous reductive depolymerization of polyesters and polycarbonates with hydroboranes is achieved with the use of an f-metal complex catalyst. These polymeric materials are transformed into their value-added alcohol equivalents. Catalysis proceeds readily, under mild conditions, with La[N(SiMe3)2]3 (1 mol%) and pinacolborane (HBpin) and shows high selectivity towards alcohols and diols, after hydrolysis.

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

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.