Abstract
The asymmetric hydroformylation of styrene using [(CO)2Rh(acac)]/(R,S)‐BINAPHOS as catalyst precursor occurs smoothly in the presence of compressed CO2 to give appreciable asymmetric induction (ee = 66% (R)) under conditions close to the critical data of pure CO2, but very low ees are obtained at high CO2 densities. The phase behaviour of the reaction medium and the different solubilities of the unmodified and ligand‐modified catalytically active species in the supercritical phase provide a possible rationalisation of the results.
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