$1 doesn't have a value when you define %triggers. You can postpone the evaluation of your string using a sub:

#!/usr/bin/perl -w
use strict;

my %triggers =
(
  'You are (\\w+).' => sub { "Your status is: $1" },
);

my $buff = "You are fired!";

foreach my $trigger ( keys ( %triggers ) )
{
  if ( $buff =~ /$trigger/ )
  {
    #print "Memory contents of \$1: $1\n";
    print &{$triggers{$trigger}};
  }
}
print "\n";
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