You can't use "Unity 2D" mode with 3D characters, because the SortingMap is for sprites only. However, you have other options:
Set your "Moving and turning" property in your Settings Manager to "World Space" - this 2D mode will cause characters (sprites and models) to move in World Space, rather than scaling for a depth effect.
Set your "Camera perspective" to 2.5D. This is the recommended workflow for 2.5D games (3D characters on 2D backgrounds) - this video tutorial covers the whole process.
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