You don't want all synchronous shifts. The 3-5 IS a synchronous shift. You want non-synchronous, like the 1-2 and 5-6.
The 1-2 applies the overdrive clutch. It's totally non-synchronous.
The 2-3 releases the overdrive and applies the intermediate. Each of these events take about 400 milliseconds to complete. If one finishes before the other by a difference of more than 0.030 seconds the shift is going to suck. If the overdrive releases before the intermediate is on the trans goes back to first gear, then shifts 1-3. You'll get an engine speed flare and damage the intermediate clutch. If the intermediate applies before the overdrive releases you now have shifted 2-4, then when the overdrive finishes it's release you go back to third gear. The intermediate won't last long doing that, either.
The 3-5 is a synchronous shift. It also takes about 0.400 seconds, and once again it's two clutches that have to finish what they are doing within about 0.030 seconds of each other. If the intermediate releases before the direct applies the trans goes back to first gear again and then shifts 1-5. The direct can only do this a couple times MAX and then it's burnt to a crisp. If the direct applies before the intermediate releases you have a tie up. This is as bad as it gets. All elements of the planetary are held from turning. The output shaft stops turning RIGHT NOW and so do the rear wheels. If you have enough power going into the transmission something mechanical will break. Pieces may go through the pan and the case. It will be catastrophic.
The 5-6 shift is identical to the 1-2. The overdrive clutch applies.
Fourth gear is third gear with the overdrive applied. If you shift 1-2-3-4-6 you change the 3-4 to a non-synchronous shift. But then the 4-6 is synchronous, it is the 3-5 but the overdrive clutch is on and stays on, so it is not part of the shift.
To go from 2-4 you keep the overdrive on and bring on the intermediate. That would be non-synchronous. 1-2-4-6 would be non-synch, non-synch, synch.
I haven't heard of anyone successfully programming a PCS to make a 5R110 shift. Frankly I'd be very surprised if it has the computer power and the required inputs to make this happen, not to mention someone with the programming knowledge to make all of this happen.
Good luck with this project. I'm interested to see how you do this and if you can make it work.