The level structure of 5422Ti32 has been explored for the first time by combining β-decay measurements from fragmentation products with prompt γ-ray spectroscopy following deep inelastic reactions. The latter technique was also instrumental in tracing 52Ti30 to higher spin. The data provide new tests of effective interactions for full pf-shell calculations in neutron-rich nuclei above 48Ca. The data indicate the presence of a significant subshell gap at N=32 and comparisons between theory and experiment suggest an additional shell closure at N=34 in Ca and Ti isotopes.