Catalytic alkene and alkyne hydroacylation using Rh(I) complexes with diphosphanes

Abstract

This TFG describes the synthesis and characterization of two short-bridged diphosphanes 𝐋𝟏 and 𝐋𝟐 Ligand 𝐋𝟏 is a novel chiral P-stereogenic methylene-bridge diphosphane that has been prepared in optically pure form. This TFG also details its complexation with rhodium(I)-diene moieties to furnish complexes 𝐂 𝟏 𝟏 and 𝐂 𝟐 𝟏 , which have been thoroughly characterized, including the crystal structure for 𝐂 𝟏 𝟏 . In addition, the stable catalytic precursor 𝐂 𝟓 𝟏 , has been also prepared and characterized, along with other Rh(I) complexes.Ligand 𝐋𝟐 is a rigid diphosphane with a fluorene-substituted methylene bridge that has been prepared following the literature procedure. The complexation of the ligand with rhodium(I) precursors has not produced the expected complexes and the interesting species formed, which remain speculative, will be the object of further studies.Moreover, in this TFG is described the synthesis of 𝐂 𝟏 𝟎 , a new bis(phosphane) complex, which has been fully characterized. Alongside with 𝐂 𝟏 𝟏 , these compounds have been tested as precursors in enantioselective hydrogenation, achieving high conversions, but moderate enantioselective excess. Complex 𝐂 𝟓 𝟏 has been used as a catalytic precursor in intermolecular hydroacylation, furnishing good activity and selectivity results for terminal and internal unsaturated substrates.