Let the required sum be $S(x)$,
$$\begin{align*}
S(x) &= \sum_{k=1}^{n} \frac{\sin(2k-1)x}{2k-1}\\
S'(x) &= \sum_{k=1}^{n} \cos(2k-1)x\\
&= \Re \left[\sum_{k=1}^ne^{i(2k-1)x}\right]\\
&= \Re \left[e^{ix}\cdot\frac{1-e^{i2nx}}{1-e^{i2x}}\right]\\
&= \Re \left[e^{inx} \cdot \frac{e^{-inx} -e^{inx}}{e^{-ix} - e^{ix}}\right]\\
&= \Re\left[(\cos nx +i\sin nx)\cdot\frac{\sin nx}{\sin x}\right]\\
&= \frac{\sin 2nx}{2\sin x}
\end{align*}$$
Since $S(x) = S(\pi-x)$, it is sufficient to consider only $x \in (0,2\pi/4]$.
In the range $x\in(0,2\pi/4]$, $S'(x)$ has the same sign as $\sin 2nx$. Local minima of $S(x)$ (including the boundary case $x=0$) are at
$$\begin{align*}
2nx &= 2\pi k\\
x &= \frac{m}{2n}\cdot 2\pi, &&0\le m\le \frac n2,\quad m\in \mathbb N
\end{align*}$$
The difference between two adjacent local minima is
$$\begin{align*}
D &= S\left(\frac{m}{2n}\cdot 2\pi\right) - S\left(\frac{m-1}{2n}\cdot 2\pi\right)\\
&= \int_{\frac{m-1}{2n}\cdot 2\pi}^{\frac{m}{2n}\cdot 2\pi}S'(x)\ dx\\
&= \int_{\frac{m-1}{2n}\cdot 2\pi}^{\frac{m}{2n}\cdot 2\pi}\frac{\sin 2nx}{2\sin x}dx\\
&= \int_{\frac{m-1}{2n}\cdot 2\pi}^{\frac{m-1/2}{2n}\cdot 2\pi}\frac{\sin 2nx}{2\sin x}dx + \int_{\frac{m-1/2}{2n}\cdot 2\pi}^{\frac{m}{2n}\cdot 2\pi}\frac{\sin 2nx}{2\sin x}dx\\
\end{align*}$$
The numerator $\sin 2nx$ is positive in the first integral, and negative in the second integral. Using the fact that $\sin x$ is increasing in $x\in(0,2\pi/4]$,
$$\begin{align*}
D &> \frac{\int_{\frac{m-1}{2n}\cdot 2\pi}^{\frac{m-1/2}{2n}\cdot 2\pi}\sin 2nx\ dx}{2\sin \frac{m-1/2}{2n}\cdot 2\pi} + \frac{\int_{\frac{m-1/2}{2n}\cdot 2\pi}^{\frac{m}{2n}\cdot 2\pi}\sin 2nx\ dx}{2\sin\frac{m-1/2}{2n}\cdot 2\pi}\\
&= \frac{\int_{\frac{m-1}{2n}\cdot 2\pi}^{\frac{m-1/2}{2n}\cdot 2\pi}\sin 2nx\ dx + \int_{\frac{m-1/2}{2n}\cdot 2\pi}^{\frac{m}{2n}\cdot 2\pi}\sin 2nx\ dx}{2\sin\frac{m-1/2}{2n}\cdot 2\pi}\\
&= 0
\end{align*}$$
In other words, the values of $S$ at $x = 0, \frac{2\pi}{2n}, \frac{2\cdot 2\pi}{2n}, \cdots, \frac{\lfloor n/2\rfloor\cdot 2\pi}2$ are strictly increasing compared with the previous one, so they are all greater than $S(0) = 0$. Also, since these $x$'s are local minima, every other $x$ between them will also be greater than $S(0) = 0$.