A process for producing isopentane and isoamylene can comprise passing a feed stream comprising C5 hydrocarbons through a hydrodesulfurization assembly to produce a first stream: passing the first stream to a first separation assembly to produce a second stream and a first separated stream: passing the second stream to a deisopentanizer assembly to produce a second separated stream comprising isopentane, a third separated stream comprising C6+ hydrocarbons, and a raffinate stream comprising C5 hydrocarbons; and passing the raffinate stream to a reactor assembly to produce a reaction product stream comprising isoamylene. The present disclosure also provides for a system for producing isopentane and isoamylene.