Unfortunately, I cannot close this question as a duplicate, since the same question appeared on mathoverflow:
https://mathoverflow.net/questions/53119/volumes-of-n-balls-what-is-so-special-about-n-5
To summarize, the answers there show that the choice to measure the dimensionless $V_n(R)/R^n$ is in fact arbitrary, and one can create other dimensionless quantities with different maximum $n$, though all will eventually decrease quickly to zero. Particularly for the case of the volume ratio of the ball to it's enclosing cube, user @Marty points out that:
More interesting geometrically might be the equally dimensionless ratio
$V_n(R)/(2R)^n$, which is the ratio of the volume of the $n$-ball to the
volume of the smallest $n$-cube containing it. This is monotonic
decreasing (for $n≥1$), showing that balls decrease in volume relative
to their smallest cubical container, as the dimension increases.
As to proving this arbitrary value, $$V'(n) = 0 \rightarrow (\ln \pi) \pi^{n/2} \Gamma(n/2+1) - \pi^{n/2}\Gamma(n/2+1)\psi_0(n/2+1)=0$$
$$\ln \pi= \psi_0(n/2+1)$$
Since the digamma function is monotonically increasing (when $n>0$), there can only be one solution, which numerically can be found at $n\approx5.26$. You can now check which of $n=5,6$ is the highest integer value.