of all people, who would have thought?
Expresses surprise or disappointment that a particular person, who was least expected to do so, did something, or that an expected action turned out differently.
This pattern is used when someone you trusted or expected to behave in a certain way does the opposite, or when an unexpected result occurs. It conveys a sense of shock, betrayal, or irony. The phrase としたことが literally means 'that (person) who did...' but is used as an interjection-like clause before stating the surprising fact.
It often appears at the beginning of a sentence or after a short pause, emphasizing the unexpectedness. For example, if a reliable friend forgets your meeting, you might say 'あの彼としたことが、約束を忘れるなんて' (Of all people, he forgot our appointment). The pattern is formal and literary, commonly found in written narratives or reported speech rather than casual conversation.
Note that it is not used for positive surprises; it typically expresses negative surprise or disappointment. Also, the subject is usually a specific person (or a group) that you have expectations about.