LaLiga giant Madrid reportedly want more than €40million for playmaker James, who has spent the past two seasons on loan at Bayern Munich.
Coach Carlo Ancelotti is eager to be reunited with the player he coached in Spain and Germany, but a stalemate in negotiations is said to have alerted Atletico Madrid.
Napoli is remaining calm, with De Laurentiis confident the Colombia international favours a switch to Stadio San Paolo.
"Carlo likes him very much and we're waiting for a more reasonable demand," De Laurentiis said.
"The obstacle is Real Madrid, who are asking for too much in our opinion.
"But James wants to come to Napoli."
Mauro Icardi is one player who will not be joining Ancelotti's side, despite the striker being told he can leave Inter.
De Laurentiis acknowledged he enquired about the Argentina international, but found him to be set on joining Serie A champion Juventus, and the Napoli chief will not entertain a swap deal involving Lorenzo Insigne.
"[Icardi] will always want to go to Juventus," he said.
"Anyway, I prefer Insigne, because we need him, and then we have [Arkadiusz] Milik and [Dries] Mertens.
"We can't ignore Icardi's talent, he's a very strong player, but we've talked about him so much now that he looks older than 26."