The 4Runner isn't like a Tacoma.
2 issues with your idea, while it is a good one.
1) relocating the exhaust is some what of a PITA. You'd have to run it right under the frame rail and exit the side of the truck, right by the door.
Nothing wrong with that, but it's just bad placement. The frame rail would crush the exhaust if you ever went wheeling and hit something. That, and it would be right by the door. Leaving the truck running, and opening the door to load something or anything like that will let hte exhaust get into the car. No big deal, but most people don't want to smell it. In most states, it is illegal to run no muffler. Maybe not yours, but IDK. The size of the muffler and cat would prohibit such a modification. Aftermarket is always an option, but again, the size of them is the limiting factor here.
2) The 4Runner fuel tank mounting is a major PITA. You have to fab up a bracket here and there, then use the second frame support to bolt the front of the fuel tank to. The strap is has one bracket that is welded to the frame, and the other that is welded to the tube cross member of the back part of the frame. IOT mod up a gas tank in the second location, you'd have to do all that over.
Then you have the issue of filling the tank. How are you going to fill it mounted on the other side of the truck? Running a secondary fill tube from the promary tank isn't going to be easy. You have all your stuff there for the drive shaft and such.
A main reason why it's so hard to relocate the gas tank, and why many people haven't done it, is that you have to take the body off the frame IOT get to the gas tank, THE EASIEST WAY. With a Tacoma, it's 6-8 bolts, and the bed comes off. Then you can just to to town. Can't do that with the Runner.
My suggestion to you, would be to take the spare out, and add a F150 tank. Make it so the F150 tank drains into the stock tank. That will give you ABOUT 36 gal total.
If that doesn't sound good to you, you can always add a fuel cell or something else to the trunk, or just carry a bunch of gas cans.....3