The advantages of modularity inherent to the DuPHOS
ligand series became apparent during attempts to hydro-genate enamides4possessing twoâ-substituents (R
1
,R
2
*H). Enantioselective hydrogenation of tetrasubstituted
alkene units of this type had presented a significant
challenge for all known catalysts, and the highest selectiv-ity reported prior to our work was 55% ee using a
DIPAMP-Rh catalyst.
We found that the rates and
enantioselectivities were dramatically dependent upon the
properties of the phospholane ligand.
In contrast to the
pre-eminence of Et-DuPHOS-Rh for enamides containing
a singleâ-substituent, sterically less encumbered catalysts
were required for hydrogenation of sterically congested
â,â-disubstituted enamides. In particular, the Me-Du-PHOS-Rh and more electron-rich Me-BPE-Rh catalysts
have been found superior for the production of multi-farious â-branched amino acids.