Unions can be used as a somewhat safer (not safe by any means but safer), more flexible, and less error-prone form of transmute. Notably you can use unions to transmute between a large type and a smaller type.
That is essentially the motivation, primarily in the context of FFI where matching C's union behaviour using transmute is tricky and error-prone.
There are rare cases where all attributes of the C union are valid at the same time. Say you have a 32-bit RGBA color value and you want to access the individual 8 bit values. You can make a union of an 32 bit int and a struct that contains 4x 8 bit integers.
Also you can manually tag them and get s.th. more like other high level languages. It will just look ugly.