No. Psychopathy is very different. In some ways psychopaths fail to process inhibitions that prevent them from revealing deceptions under high stress conditions. Its not clear what difference in the brain allows that behavior in that context as it eliminates several forms of standard processing, but it is known that psychopathy is a neurological disorder directly aligned with extreme narcissism.

People with a natural ability to process naturally through high fear stimulus still feel fear. Unlike psychopaths these high risk people still exhibit all the same physical symptoms of a stress/fear response. The difference is that they lack just the emotional inhibition associated with that fear response. In normal people a fear stimulus drives us to halt, pause, and evaluate our options. This processing takes time and when it becomes crippling its called anxiety.

People capable of processing through extremely high risk are not so inhibited. Either they are powering through the risky scenarios intentionally as a means of learning something new or because they have weighed their options and found the high risk approach to support an outcome with value that exceeds that severity and and incidence of associated risk.

Here is an example. Imagine deploying as a military service member to Afghanistan at the height of that conflict knowing rockets and bombs land on bases that hurt people. This sounds high risk, because you certainly don't encounter this ever driving to work in the US. Evidence will indicate, though, at that time a person was 10x more likely to die from a traffic accident driving to work or from being shot by police in the US than they were to die from any reason while serving in Afghanistan. Most people are not capable or appreciating that. Now apply that same line of critical thinking to modifications of your daily routine. A for a high risk person this is common and boring while for everybody else its extremely challenging and quite stressful. These are not the kind of people tempted to explore drug use.