We report on the first measurement of cross sections for exclusive deeply virtual pion electroproduction off the proton, $e p to e^prime n pi^+$, above the resonance region at backward pion center-of-mass angles. The $varphi^*_{pi}$-dependent cross sections were measured, from which we extracted three combinations of structure functions of the proton. Our results are compatible with calculations based on nucleon-to-pion transition distribution amplitudes (TDAs) and shed new light on nucleon structure.