We have
$$
\eqalign{
1&=f(1)-f(0)=\int_0^1 f'(x)\,dx\cr
&=\int_0^{1/2}f'(x)\,dx+\int_{1/2}^1 f'(x)\,dx\cr
&=\int_0^{1/2}\int_0^xf''(t)\,dt\,dx-\int_{1/2}^1 \int_x^1f''(t)\,dt\,dx\cr
&=\int_0^{1/2}(1/2-t)f''(t)\,dt-\int_{1/2}^1 (t-1/2)f''(t)\,dt.\cr
}
$$
Consequently, if $|f''(t)|\le 4$ for all $t\in[0,1]$, then by the above and the triangle inequality,
$$
\eqalign{
1&\le 4
\int_0^{1/2}(1/2-t)\,dt+4\int_{1/2}^1(t-1/2)\,dt\cr
&=-2(1/2-t)^2\Big|_0^{1/2}+2(t-1/2)^2\Big|_{1/2}^1\cr
&=1/2+1/2=1.\cr
}
$$
It follows that
$$
\int_0^{1/2}(1/2-t)|f''(t)|\,dt=\int_{1/2}^1 (t-1/2)|f''(t)|\,dt=1/2,
$$
which togetther with the hypothesis $|f''(t)|\le 4$ for all $t$ implies that $|f''(t)|=4$ for all $t\in[0,1]$. As $f''$ is continuous, we must have either $f''(t)=4$ for all $t$ or $f''(t)=-4$ for all $t$. In the first case $f(x)=2x^2$ in violation of $f(1)=1$. Likewise the second alternative leads to a contradiction.