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大きな is part of a *small series* of words where you can remove the い from an い adjective and add な. None of these work as full な adjectives, so you can’t say あの家は大きだ. You can’t say 大き家 either, by the way, only 大きな家 or 大きい家. And you can’t make new ones. Off the top of my head there’s also 小さな and おかしな. I think there are one or two more but they’re not coming to mind.
There isn’t a huge difference between 大きな and 大きい before a noun but 大きな has more of a subjective feeling, slightly.
It’s not a general rule. I’ve always thought of them as special cases. See [here](https://japanese.stackexchange.com/questions/1853/i-adjectives-used-as-na-adjectives-is-there-a-difference-e-g-%e5%a4%a7%e3%81%8d%e3%81%84-versus-%e5%a4%a7%e3%81%8d%e3%81%aa) for a more complete analysis.
“〜な” is simply used to form the attributive form of what in Japanese are called “descriptive verbs” [形容動詞] but one may encounter in English are “na adjectives”, “adjectival nouns”, “na-verbs”, “nominal verbs” and so forth.
Essentially, Japanese has “attributive clauses”. Sentences that modify nouns similar to relative clauses in English, as in for instance “the park **that I walk in**”. In Japanese these come before the noun, so we have “**私が歩く**公園” for the same thing.
In older forms of Japanese, the forms verbs took differed more depending on whether they were used in attributive clauses or main clauses. One of the few remnants of that is that in the nonpast form, descriptive verbs are suffixed with “〜な” in attributive clauses, and with “〜だ” in main clauses. So “That person is the prettiest in the room.” becomes “その人は部屋で一番綺麗**だ**。” but “the person **who is the prettiest in the room**” becomes “部屋で一番綺麗**な**人”. With most other verbs this does not change in any way, as with the situation of walking in the park.
It should be added that “大きな” is irregular. It actually mostly belongs to a different class of verbs that takes “〜い”, to form both forms but for this form only, it can also be conjugated with “〜な” optionally, but using “大きい家” is fine as well.
So again, we can say “その家は町で一番大き**い**。” to mean “That house is the biggest in the town.” or we can say “町で一番大きい家”, but “大きい” is unique in that “大きな” can also be used in the latter case.
We can of course also simply say “綺麗な人” to mean “a person who is pretty” or just “pretty person”. Japanese does not have the distinction between “adjectives” and “relative clauses” that English has. An attributive clause with only a single simple verb like “to be pretty” here functions that way.
I think you might be confusing い adjectives and な adjectives over an irregular case. [This](https://www.youtube.com/watch?v=1VwyXw1gUwA) is the best video I’ve seen covering how both these forms work, which was used to cover how it was taught in Genki and how that probably isn’t the best way to learn.
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[A brief summary](https://www.kanshudo.com/grammar/%E9%80%A3%E4%BD%93%E8%A9%9E) on why 大きな is irregular.
>What does the な
Think of it as similar to だ, but you use it before a nown. しずかだ (it’s quiet) -> しずかな町 (a town that is quiet).
The above doesn’t work for your specific example, though; you can’t say 大きだ.
です and だ are very related. Unlike the latter, です can be used after い-adjectives today, although it used to not be the case around a century ago.