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use strict;
use Data::Dumper;
...
 %{$h_ref}->{E} = '5';  # this is what it's doing
 $$h_ref{F}     = '6';  # you could do this too
}

Before sub:$VAR1 = {
          'A' => '1',
...
          'D' => '4',
          'E' => '5'
        };