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Help How do you enter a series of numbers hands free when you receive an automated phone call?

I just bought a Samsung Galaxy S5 with Lollipop (Android 5.0 OS) in part, because it has a great battery for making and receiving a high volume of phone calls. Someone told me I can enter one set of numbers hands free on an incoming call.

Ideally, I need to enter access codes followed by *s on incoming automated calls hands free.

Is it possible to do this? I am wondering about programming one button (like the power button on the right side of the phone) to bring up multi-window mode and favorites from the contacts app and possibly using a voice app like S Voice.
 
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