Another answer suggests that the two decays
\begin{align}
D^0 &\to \pi^- e^+ \nu_e & \text{BR: } & 0.291(4)\times10^{-2}
\\
D^0 & \to \pi^+ e^- \bar\nu_e & \text{BR: } & ???
\end{align}
(with branching ratio from pdgLive)
are charge-conjugates.
That was my first thought as well, but it's not correct.
The two final states are charge-conjugates.
However the charge conjugate of the $D^0$, which has quark content $c\bar u$, is the $\bar D^0$, with quark content $\bar cu$.
And that reveals why the second decay is (at least at tree level) forbidden.
In the quark model, the measured decay is the weak decay of a charm quark,
$$
c \to d e^+ \nu_e,
$$
with the $\bar u$ along for the ride.
To have the quark content change from $c\bar u = D^0$ to $\bar d u = \pi^+$, as you propose, is a much messier suggestion if it's even possible at all.