Working over $\mathbb C$, let's write $B$ as a block matrix
$$ B = \begin{bmatrix}0 & X \\ E & 0 \end{bmatrix} $$
Then
$$ B^2 = \begin{bmatrix}XE & 0 \\ 0 & EX\end{bmatrix} $$
and since $XE$ and $EX$ have the same eigenvalues, we can do a case analysis on the number of these eigenvalues:
If there's only one eigenvalue for $EX$ and $XE$, then $B^2$ has only one eigenvalue. However, Wolfram Alpha tells us that $A^2$ has three different eigenvalues, so $A$ cannot be similar to such a $B$.
On the other hand, if $EX$ has two eigenvalues, it is diagonalizable, and so is $XE$, so $B^2$ is diagonalizable. But Wolfram Alpha just showed us that $A^2$ isn't diagonalizable, so $A$ is not similar to this kind of $B$ either.
Since $A$ is not similar to any $B$-shaped matrix over $\mathbb C$, this is in particular not the case over $\mathbb R$ either.