Ooh, this is one of my favorite tropes!!! Love stories where the main villain only has a soft spot for the female lead...
Here are two of my favorite series with this kind of character (both villains were the ultimate big bad and not second-in-commands and both heroines never reciprocated their feelings):
Harper's Island (non-asian horror TV series):
The villain is 100% yandere. He's sadistic and duplicitous, basically manipulating all the events and killing everyone that'll stand in the way of him and the heroine. Everything he does is so that he can be with the heroine in the end, just the two of them "forevermore." Loved this series and loved him...I'm a total sucker for yandere villains (real villains, esp. the ultimate baddie, not mere mean bullies, etc.).
Memory Lost (Chinese drama):
The villain's backstory and motivations were so compelling that my heart was absolutely shattered in the end. He really took obsession to the next level (erases the heroine's memories so he can start over with her) and I can't say he loved the heroine any less than the hero -she really was his entire world! He could give up anything and anyone in order to be with her. Even the other woman said it, "I knew an old friend who could turn against the whole world in order to possess the one thing he wants..."
Honorable mention:
Missing You -The main villain is gorgeous and obsessively in love with the female lead. But I haven't watched the whole drama, so can't attest to its overall quality. But I know it's got what you're looking for.