MaxPHOS Ligand: PH/NH Tautomerism and Rhodium- Catalyzed Asymmetric Hydrogenations

EDGAR CRISTÓBAL-LECINA; PABLO ETAYO; SAN DORAN; MARC REVÉS; PABLO MARTN-GAGO; ARNALD GRABULOSA; ANDREA R. COSTANTINO; ANTON VIDAL-FERRAN; ANTONI RIERA; VERDAGUER

ADVANCED SYNTHESIS & CATALYSIS (PRINT)

WILEY-V C H VERLAG GMBH

Lugar: Weinheim; Año: 2014 vol. 356 p. 795 - 804

1615-4150

MaxPHOS is an active and robust P-stereogenic ligand for asymmetric catalysis. The presence of an [BOND]NH[BOND] bridge between the two phosphine moieties allows the NH/PH tautomerism to take place. The neutral ligand, in which the NH form predominates, is an air-sensitive compound. However, protonation of MaxPHOS leads to the stable PH form of the ligand, in which the overall positive charge is distributed on both P centers. This protonation turns the MaxPHOS⋅HBF4 salt 3 into an air-stable compound both in the solid state and in solution. The salt 3 is also a convenient precursor for the preparation of rhodium(I) complexes by direct ligand exchange with the complex [Rh(acac)(cod)]. Finally, the corresponding rhodium(I)-MaxPHOS complex was tested in the asymmetric hydrogenation of a wide range of substrates. The complex proved to be a highly selective and robust system in these reactions.