Effect of the CO2H groups of carboxylated triarylphosphines on (COD) RhCl(PAr3) -catalyzed isomerization of 1-octen-3-ol under phase transfer conditions

Article abstract of DOI:10.1016/S1381-1169(96)00374-3

Water soluble sodium salts of (COD)RhCl(PAr₃), where PAr₃ is Ph₂P(C₆H₄-2-COOH), Ph₂P(C₆H₄-3-COOH), Ph₂P(C₆H₄-4-COOH), PhP(C₆H₄-3-COOH)₂, or P(C₆H₄-3-COOH)₃, catalyze under phase transfer conditions the isomerization of 1-octen-3-ol to 3-octanone. The reaction rate depends on the position and number of the carboxyl groups in the phosphine ligand. (COD)RhCl[Ph₂P(C₆H₄-2-C₆H₄-COOH], which exists as an equilibrium mixture with (COD)(H)RhCl(-OCOC₆H₄-2-PPh₂) more reactive than the hydride-free catalysts. A hydride addition-elimination mechanism is suggested as the major pathway for the catalytic process.