You could replace all that preceed a word character with the left quote, and all that follow a word character with a right quote.
str = str.replace(/"(?=w|$)/g, "“");
str = str.replace(/(?<=w|^)"/g, "”"); // IF the language supports look-
// behind. Otherwise, see below.
As pointed out in the comments below, this doesn't take punctuation into account, but easily can:
/(?<=[w,.?!)]|^)"/g
[Edit:] For languages that don't support look-behind, like Javascript, as long as you replace all the front-facing ones first, you have two options:
str = str.replace(/"/g, "”"); // Replace the rest with right curly quotes
// or...
str = str.replace(/"/g, "”"); // Replace any quotes after a word
// boundary with right curly quotes
(I've left the original solution above in case this is helpful to someone using a language that does support look-behind)
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