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When i start approval workflow with selected users, after can i add new users to current process?
Natively, you can reassign or delegate the task, but this does not really add users to the workflow.
Otherwise, you can create / override a workflow based on the approval one and customize the form, adding a User Suggestion Widget that will append user(s) to the assignees of the workflow. I did that along with a checkbox letting the user choose if he wants to be notified at the end of the workflow.
Is it possible to add via api?
All elements in a workflow are documents, you can have a look at RouteNode, DocumentRoute, etc.