Let $M$ be a Riemannian manifold and let $\nabla$ be a connection compatible with the metric. Then for any vector fields $V,W$ along the smooth curve $c:I\rightarrow M$ , we have
$\frac{d}{dt}\langle V, W\rangle =\langle \frac{DV}{dt},W\rangle+ \langle V, \frac{DW}{dt}\rangle$
However my question is: Why does $\frac{d}{dt} \langle V, W \rangle$ make sense?
$V$ and $W$ are vector fields along a curve, so I suppose $\langle V, W\rangle$ is viewed as a map $I\rightarrow \mathbb{R}$ , where $\langle V,W \rangle(t)=\langle V_t, W_t \rangle$ . But how do we show that it is smooth? Also compatibility of the metric is defined on smooth vector fields.
If $M$ is a smooth manifold then $TM$ also has a natural smooth structure, hence, does $E=TM\times TM$. The projection $\pi: TM\to M$ defines a smooth map $$ \pi\times \pi: E\to M^2. $$ I will leave it to you to verify that the preimage of the diagonal under $\pi\times \pi$ is a smooth submanifold $A$ in $E$. Explicitly: $$ A=\{(u,v)\in TM\times TM: \pi(u)=\pi(v)\}, $$ i.e. $A$ consists of pairs of vectors in the same tangent space $T_pM$, $p\in M$.
A Riemannian metric $g$ on $M$ is a smooth function $g: A\to {\mathbb R}$ (satisfying further linearity conditions which are irrelevant for us). Given a curve $c: I\to M$, a vector field $X$ along $c$ is a smooth map $X: I\to TM$ such that $\pi\circ X=c$. A pair of such vector fields $X, Y$ defines a smooth map $P: I\to A$. Hence, the composition of two smooth maps $g\circ P$ is again smooth. This composition is nothing but the function $$ t\mapsto g(X,Y)(t), t\in I. $$