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MAdPHOS, a P‑Stereogenic Aminodiphosphane Ligand withAdamantyl Groups: Synthesis, NH/PH Tautomerism, and Rhodiumand Nickel Complexes.
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A novel chiral ligand, named MAdPHOS, bearing aP-stereogenic phosphane and a diadamantyl phosphane linked by aNH bridge has been synthesized. This bulky, C1-symmetric, PNPligand has been prepared from enantiopure tert-butylmethylaminophosphane and was obtained as a crystalline solid. TheNH/PH tautomerism, air-stability, and σ-donor capacity ofMAdPHOS have been assessed herein. The free ligand has beenprepared, showing much higher stability, in the solid form, than itstert-butyl analogue MaxPHOS. Both rhodium and nickel CODcomplexes have been prepared. The Rh-MAdPHOS complex hasshown outstanding enantioselectivities in the asymmetric hydrogenationof enamides.
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BELLIDO, Marina, et al. MAdPHOS, a P‑Stereogenic Aminodiphosphane Ligand withAdamantyl Groups: Synthesis, NH/PH Tautomerism, and Rhodiumand Nickel Complexes. Journal of Organic Chemistry. 2025. Vol. 90, num. 5, pags. 1794-1800. ISSN 0022-3263. [consulted: 24 of May of 2026]. Available at: https://hdl.handle.net/2445/229445