Step 1: Impose the defining conditions directly. Let $\vec{a}^{*}=(p,q)$ in the $(\hat{i},\hat{j})$ basis.
Step 2: Orthogonality to $\vec{b}=2\hat{j}$: $\vec{a}^{*}\cdot\vec{b}=2q=0$, so $q=0$. Hence $\vec{a}^{*}$ points purely along $x$.
Step 3: Normalization with $\vec{a}=2\hat{i}+\hat{j}$: $\vec{a}^{*}\cdot\vec{a}=2p+q=2p=2\pi$.
Step 4: Solve $2p=2\pi\Rightarrow p=\pi$.
Step 5: Assemble the vector.
\[\boxed{\vec{a}^{*}=\pi\hat{i}}\]