Selektive Homogenkatalyse in Mehrphasensystemen. Teilprojekt: Synthese massgeschneiderter Phosphane mit polarer Peripherie fuer die Mehrphasenkatalyse Schlussbericht

New alkyl-and arylphosphine ligands with polar peripheries (OH, COOH and PO_3"2"- groups) for application in multiple phase catalysis have been obtained. Ligand tailoring was achieved using different and complementary synthetic procedures (nucleophilic phosphination and Pd catalyzed P-C coupling reactions) developed by us. Thus consecutive Pd catalyzed P-C coupling reactions afforded chiral and achiral aromatic secondary and tertiary phosphines containing COOH and PO_3"2"- substituents. Chemo- and steroselective ring opening reactions of (R)-glycidol or nucleophilic phosphination of (R)-solketal-tosylate gave enatiomerically pure phosphines. Using analogous secondary phosphines as starting materials chelate ligands with homochiral #beta#-carbon atoms are accessible which are of interest as catalyst components in enantioselective syntheses of organic intermediates. The structures of phosphine ligands with polar peripheries (OH, COOH and PO_3"2"-) have been obtained by X-ray structural analysis which, together with the results of detailed NMR investigations, provided useful information for a modelling of their catalyst complexes. Phosphines containing phosphonato groups turned out to be very active catalyst ligands in Pd mediated two-phase telomerization of butadiene and isoprene with water and methanol as well as in multiphase Suzuki-type coupling reactions leading to biaryls and heterobiaryls which are important fine chemicals. (orig.)SIGLEAvailable from TIB Hannover: DtF QN1(72,42) / FIZ - Fachinformationszzentrum Karlsruhe / TIB - Technische InformationsbibliothekBundesministerium fuer Bildung, Wissenschaft, Forschung und Technologie, Bonn (Germany)DEGerman