Dear @OluJacob ,
You can do voluntary work or vocational training while still in the asylum process. For voluntary work you do not need permissnio from the Ausländerbehörde. For vocational training you need to have been at least three months in the asylum process and you have to ask permission to do the training from the Ausländerbehörde.
I'm not based in Munich so I do not know of any specific companies. But I recommend you **** through this list of resources for assistance finding work in Munich:
For help finding somewhere to volunteer, you can have a **** at these organisations: