Esta regex faz o trabalho:
^(?:(?!cmd\.exe).)*$
Explicação:
^ : begining of string
(?: : start non capture group
(?! : start negative lookahead
cmd\.exe : literally (you may add wordboundaries \bcmd\.exe\b if you don't want to match mycmd.exe)
) : end lookahead
. : 1 any character but newline
)* : end group, repeated 0 or more times
$ end of string
Exemplos:
C:\Windows\System32\cmd.exe --> Doesn't match
C:\Windows\System32\mycmd.exe --> Doesn't match without wordboundaries, else Match
C:\Windows\System32\cmd --> Match
C:\Windows\System32\exe --> Match