During the optimization of the hydroamination reaction we observed that raising the temperature favoured the hydrolysis of the imine to yield 3-hydroxyketone, so optimized conditions were developed to access the this latter product efficiently. We hypothesized that in situ imine hydrolysis would liberate the aniline, allowing it to participate in further hydroamination reactions. It should therefore be possible to achieve the reaction with a substoichiometric quantity of amine. After examining a small selection of anilines in combination with the gold catalyst (Supporting information), 3-trifluoromethylaniline was identified as a suitable co-catalyst. With these conditions in hand we explored the scope of the hydroamination/hydrolysis reaction for preparing 3-hydroxyketones (Scheme 4). The reaction shows excellent functional group tolerance in terms of substituents on the propargylic alcohol, including cyclic structures (2c, 3c, 16c and 21c) and bulky groups (4c). The reaction is compatible with primary (24c and 25c), secondary (1c-4c, 6c-12c, 15c-17c), tertiary (5c, 13c, 18c, 20c and 22c) as well as benzylic (9c-13c, 15c, 16c and 19c) propargylic alcohols, even though the latter substrates are often prone to elimination of water to give the corresponding enones. Scheme 4 Synthesis of 3-hydroxyketones via catalytic hydroamination of propargylic alcohols with in situ imine hydrolysis. In other solvents, the yields of 1a obtained were: MeCN (88%), PhF (86%), MeOCO2Me (85%), PhMe (88%), EtOAc (82%); Larger scale reaction (5 mmol); 0.5 eq of aniline used; Reaction carried out at room temperature for 40 h.