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Updated: May 30, 2025

The Synthesis, Characterization and Reactivity of a Series of Ruthenium N-triphosPh Complexes
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MAdPHOS, a P-Stereogenic Aminodiphosphane Ligand with Adamantyl Groups: Synthesis, NH/PH Tautomerism, and Rhodium and
Marina Bellido1,2, Helena Solé-Àvila1,2, Martí Sidro1,2
1Institute for Research in Biomedicine (IRB Barcelona). The Barcelona Institute of Science and Technology (BIST), Baldiri Reixach 10, 08028 Barcelona, Spain.
Abstract:
A novel chiral ligand, named MAdPHOS, bearing a P-stereogenic phosphane and a diadamantyl phosphane linked by a NH bridge has been synthesized. This bulky, C1-symmetric, PNP ligand has been prepared from enantiopure tert-butylmethyl aminophosphane and was obtained as a crystalline solid. The NH/PH tautomerism, air-stability, and σ-donor capacity of MAdPHOS have been assessed herein. The free ligand has been prepared, showing much higher stability, in the solid form, than its tert-butyl analogue MaxPHOS. Both rhodium and nickel COD complexes have been prepared. The Rh-MAdPHOS complex has shown outstanding enantioselectivities in the asymmetric hydrogenation of enamides.
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