Reductive hydroformylation with a selective and highly active rhodium amine system

•Direct synthesis of alcohols from olefins via reductive hydroformylation using Rh/trialkylamine catalysts.•Extensive study of role of the amine during the reductive hydroformylation.•Tolman-like map, linking the steric bulkiness and basicity of employed amines to their hydrogenation activity.•13C NMR and in situ-FTIR studys regarding the characteristics of the rhodium/amine catalyst.•Reaction system yielding 70% alcohols within 1.5 h (TOF of 93 h−1).