Note. At the time of writing, the accepted answer to this question was that of Douglas Zare.
The accepted answer to this question is incorrect, albeit for what appears to be a relatively minor reason. I discovered this while answering a special case of the same question over at [math.SE][1]math.SE, where it was observed that in the special case $b=3$ and $n=10$, the formula from this post gave an absurdly large value.
After consulting the literature myself, I found the correct formula in Theorem 2 of [Stadje [1990]][1] Stadje [1990] (specifically equation (2.15) therein) with $p=1$ and $l=s=n$ and $m=b$. The desired expectation equals $$ \binom{n}{b}\sum_{j=0}^{n-1}\frac{(-1)^{n-j+1}\binom{n}{j}}{\binom{n}{b}-\binom{j}{b}}. $$
Comparing this formula with the (incorrect) one from the accepted answer, we change variables in the sum to $s=n-j$, yielding
$$ \sum_{s=1}^{n}\frac{(-1)^{s+1}\binom{n}{s}}{1-\binom{n-s}{b}/\binom{n}{b}}, $$ whereas the incorrect accepted answer states $$ \sum_{s=1}^{n-b}\frac{(-1)^{s+1}\binom{n}{s}}{1-\binom{n-s}{b}/\binom{n}{b}}. $$ The only difference is in the range of the summation, and it arises due to a mistake made by the accepted answer in the $i=0$ case of the following manipulation: $$ \sum_{S\not=\varnothing}(-1)^{|S|+1}\left(\frac{\binom{n-|S|}{b}}{\binom{n}{b}}\right)^i\overset{!}{=}\sum_{s=1}^{n-b}(-1)^{s+1}\binom{n}{s}\left(\frac{\binom{n-s}{b}}{\binom{n}{b}}\right)^i. $$ The equality holds when $i\not=0$, but when $i=0$ the terms with $s>n-b$ do in fact contribute. The corrected formula reads as follows: $$ \sum_{S\not=\varnothing}(-1)^{|S|+1}\left(\frac{\binom{n-|S|}{b}}{\binom{n}{b}}\right)^i=\sum_{s=1}^{n}(-1)^{s+1}\binom{n}{s}\left(\frac{\binom{n-s}{b}}{\binom{n}{b}}\right)^i. $$ The rest of the reasoning in the accepted answer is correct, and with this fix yields the correct answer. [1]: https://math.stackexchange.com/questions/3278200/box-of-10-chocolates/3278285#3278230