This is more of a long comment than an answer, but it might offer some insight beyond what's already in Dietrich Burde's answer.
Let's rewrite the OP's inequality with a slight shift in index and then some rearrangement of terms:
$$\begin{align}
2(n-1)\lt p_{n+1}\prod_{k=3}^{n+1}\left(p_k-1\over p_k\right)
&=p_{n+1}\left(4\over5\right)\left(6\over7\right)\left(10\over11\right)\cdots\left(p_{n+1}-1\over p_{n+1}\right)\\
&=4\left(6\over5\right)\left(10\over7\right)\cdots\left(p_{n+1}-1\over p_n\right)\\
&=3\left(1+{1\over3}\right)\left(1+{1\over5}\right)\left(1+{1\over7}\right)\cdots\left(1+{(p_{n+1}-p_n)-1\over p_n}\right)
\end{align}$$
This suggests an equivalent form for the OP's question:
What values of $n$ satisfy the inequality
$${2\over3}(n-1)\lt\prod_{k=1}^n\left(1+{g_k-1\over p_k}\right)$$
where $g_k=p_{k+1}-p_k$ is the gap to the next prime?
Note that including the prime $p_1=2$ has no effect, since $1+{g_1-1\over p_1}=1+{0\over2}=1$. Note also that if the terms in the product were just $1+{g_k\over p_k}$, then the product would telescope down to $p_{n+1}\over2$, which is certainly greater than ${2\over3}(n-1)$. Even if we just drop the $-1$ from the numerator $g_k-1$ for $k$ beyond some (fixed) value $N$, the inequality would reduce to something of the form ${2\over3}(n-1)\lt C_N{p_{n+1}\over p_N}$, which would eventually be satisfied, since $p_n\sim n\log n$. So for the inequality to fail for most $n\gt5$, which is Dietrich's concluding supposition, the subtraction of $1$ from $g_k$ must continue to be significant, which suggests that a definitive answer must be based on some analysis of the prevalence of relatively small gaps between primes.