First, we split $a$ into its integral and fractional part
$$
\left\lfloor {\left( \matrix{ n \cr k \cr} \right)a} \right\rfloor
= \left\lfloor {\left( \matrix{ n \cr k \cr} \right)
\left( {\left\lfloor a \right\rfloor + \left\{ a \right\}} \right)} \right\rfloor
= \left( \matrix{ n \cr k \cr} \right)\left\lfloor a \right\rfloor
+ \left\lfloor {\left( \matrix{ n \cr k \cr} \right)
\left\{ a \right\}} \right\rfloor \quad \left| {\;0 \le \left\{ a \right\} < 1} \right.
$$
so that we get
$$
\left( \matrix{ n \cr k \cr} \right)\left\lfloor a \right\rfloor \le
\left\lfloor {\left( \matrix{ n \cr k \cr} \right)a} \right\rfloor
< \left( \matrix{ n \cr k \cr} \right)\left( {\left\lfloor a \right\rfloor + 1} \right)
$$
Then we rewrite the ratio of the binomials as
$$
\eqalign{
& {1 \over {\left( \matrix{ 2n \cr k \cr} \right)}}\left( \matrix{ n \cr k \cr} \right)
= {{n^{\,\underline {\,k\,} } } \over {k!{{\left( {2n} \right)^{\,\underline {\,k\,} } } \over {k!}}}}
= {{n^{\,\underline {\,k\,} } } \over {\left( {2n} \right)^{\,\underline {\,k\,} } }} = \cr
& = {{n^{\,\underline {\,k\,} } } \over {\left( {2n} \right)^{\,\underline {\,n + k - n\,} } }}
= {{n^{\,\underline {\,k\,} } } \over {\left( {2n} \right)^{\,\underline {\,n\,} } n^{\,\underline {\,k - n\,} } }} = \cr
& = {{n^{\,\underline {\,k\,} } }
\over {\left( {2n} \right)^{\,\underline {\,n\,} } n^{\,\underline {\,k\,} } \left( {n - k} \right)^{\,\underline {\, - n\,} } }}
= {1 \over {\left( {2n} \right)^{\,\underline {\,n\,} } \left( {n - k} \right)^{\,\underline {\, - n\,} } }} = \cr
& = {{\left( {n - k + 1} \right)^{\,\overline {\,n\,} } } \over {\left( {2n} \right)^{\,\underline {\,n\,} } }}
= {{\left( {2n - k} \right)^{\,\underline {\,n\,} } } \over {\left( {2n} \right)^{\,\underline {\,n\,} } }}
= {1 \over {\left( \matrix{ 2n \cr n \cr} \right)}}\left( \matrix{2n - k \cr n \cr} \right) \cr}
$$
where $x^{\,\underline {\,k\,} } ,\quad x^{\,\overline {\,k\,} } $ represent respectively the Falling and Rising Factorial
So the sum becomes
$$
\eqalign{
& S(n) = \sum\limits_{k = 1}^n
{{{\left( \matrix{ n \cr k \cr} \right)} \over {\left( \matrix{ 2n \cr k \cr} \right)}}}
= \sum\limits_{k = 0}^n
{{{\left( \matrix{ n \cr k \cr} \right)} \over {\left( \matrix{ 2n \cr k \cr} \right)}}} - 1 = \cr
& = \left( {{1 \over {\left( \matrix{ 2n \cr n \cr} \right)}}
\sum\limits_{0 \le \,k\;\left( { \le \,n} \right)}
{\left( \matrix{ 2n - k \cr n \cr} \right)} } \right) - 1 = \cr
& = {1 \over {\left( \matrix{ 2n \cr n \cr} \right)}}\left( \matrix{2n + 1 \cr n + 1 \cr} \right) - 1
= {1 \over {\left( \matrix{ 2n \cr n \cr} \right)}}{{2n + 1} \over {n + 1}}
\left( \matrix{2n \cr n \cr} \right) - 1 = \cr
& = {n \over {n + 1}} \cr}
$$
and you can easily conclude about the limit