The enantioselective hydrogenation of several α-keto esters (3a-f, 5a-j), α-keto amides (7a- e) and isatine derivatives (9a-d) with a set of four representative neutral homogeneous rhodium-amidophosphine-phosphinite catalysts has been investigated. Trifluoroacetato-Rh- AMPP catalytic precursors promoted the rapid, efficient synthesis of aliphatic α-hydroxy esters 4a-f in moderate to high enantioselectivities (66–95% ee), in contrast to most ...