A new type of bicyclic bridgehead phosphoramidites (briphos) is reported, where the geometrical constraints significantly enhance the π-acceptor ability compared with its monocyclic analogs. The briphos is shown to be highly efficient and tunable for Rh(I)-catalyzed conjugate additions of aryl boronic acids to α,β-unsaturated ketones and N-tosyl ketimines.
“Mother diamine” (MD) or 1,2‐bis(2‐hydroxy‐phenyl)ethylenediamine can be rapidly transformed to a wide variety of chiral ligands including vicinal diamines and analogs of binol (MDdiol), binap (MDdiphos), and monophos (MDphos). The reactivity and stereoselectivity of the MDphos ligands in Rh‐catalyzed hydrogenation are highly sensitive to the N,N′‐dialkyl substituents.
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