What you've written is pretty unclear, because the nature of $i$ and $j$ seems to be in flux. But there are basically two possibilities, each of which has a fundamental error.
The most natural interpretation of what you've written is that $i, j$ are chosen at the beginning. The choice of $i$ and $j$ determines $\mathcal{A}^*$ - pick different $i$ and $j$ and you get different systems. So for clarity let's write it "$\mathcal{A}[i,j]$" instead of "$\mathcal{A}^*$" so we can distinguish between systems coming from different $i$ and $j$.
Now the mistake reveals itself. You write "Pick $j$ such that $K(j)>L_{\mathcal{A}^*}$." This looks reasonable because the notation suggests that $\mathcal{A}^*$ is a system defined independently of $j$. But in our notation above, what you've written is $$\mbox{"Pick $j$ such that $K(j)>L_{\mathcal{A}[i, j]}$,"}$$ and now it's clear that the existence of such a $j$ needs to be proved. And, in fact, no such $j$ exists.
In fact, we can add a bit of clarity here. If we pick $i$ and $j$ such that $i>j$, then of course $\mathcal{A}$ proves $i>j$; so the system $\mathcal{A}[i,j]$ is equivalent to $\mathcal{A}\cup\{K(i)>K(j)\}$. And now it's even clearer that we can't in fact find a $j$ which works as desired.
The error above can be resolved if we interpret $\mathcal{A}^*$ as being variables which range over some set of values. One bad interpretation is as $$\mathcal{A}^*_1=\mathcal{A}\cup\{(i>j)\rightarrow (K(i)>K(j)): i,j\in\mathbb{N}\}.$$ This is silly, so let's ignore it.
We actually want $i$ and $j$ to range over reasonable values. This suggests a second interpretation: that we have $$\mathcal{A}^*_2=\mathcal{A}\cup\{(\mbox{$i-j$ is "large enough"})\rightarrow[(i>j)\rightarrow (K(i)>K(j))]: i, j\in\mathbb{N}\}.$$ This is a perfectly reasonable system; indeed, the new sentence is provable in $\mathcal{A}$ itself (as long as $\mathcal{A}$ is reasonably strong)! But this system can't actually prove any new values of $K$, since there will be a limit to the pairs $i, j$ for which $\mathcal{A}^*$ proves the appropriate largeness condition, corresponding to $L_\mathcal{A}=L_{\mathcal{A}^*}$.
Finally, we might consider the system $$\mathcal{A}^*_3=\mathcal{A}\cup\{(i>j)\rightarrow (K(i)>K(j)): \mbox{$i-j$ is "large enough"}\}.$$ This system certainly computes lots of new values of $K$; however, it's not recursively axiomatized! So Chaitin's incompleteness theorem doesn't apply.
So the problem with your argument is an ambiguity around what $\mathcal{A}^*$ is. Once we resolve this ambiguity by picking a precise definition, regardless of how we do this, a clear error emerges - either the nonexistence of the desired $j$, or the weakness/incomputability of the theory.