Preparation of a Series of Supported Nonsymmetrical PNP-Pincer Ligands and the Application in Ester Hydrogenation

Chemistry. 2019 Dec 2;25(67):15341-15350. doi: 10.1002/chem.201903379. Epub 2019 Nov 4.

Abstract

In contrast to their symmetrical analogues, nonsymmetrical PNP-type ligand motifs have been less investigated despite the modular pincer structure. However, the introduction of mixed phosphorus donor moieties provides access to a larger variety of PNP ligands. Herein, a facile solid-phase synthesis approach towards a diverse PNP-pincer ligand library of 14 members is reported. Contrary to often challenging workup procedures in solution-phase, only simple workup steps are required. The corresponding supported ruthenium-PNP catalysts are screened in ester hydrogenation. Usually, industrially applied heterogeneous catalysts require harsh conditions in this reaction (250-350 °C at 100-200 bar) often leading to reduced selectivities. Heterogenized reusable Ru-PNP catalysts are capable of reducing esters and lactones selectively under mild conditions.

Keywords: catalyst immobilization; heterogeneous catalysis; hydrogenation; pincer ligands; solid-phase synthesis.