It's a great problem!
Theorem. The mathematicians have a winning strategy in the game for every ordinal $\alpha$.
Proof. Let's prove the theorem by transfinite induction. Suppose that the mathematicians have winning strategies in the games of any particular length $\beta$ less than $\alpha$, and let us fix agreed-upon strategies for those games. Consider now the case of $\alpha$ many mathematicians. I shall describe a winning strategy. In the space of all possible assignments of hat colors to the $\alpha$ many mathematicians, define that two such assignments are equivalent $s\sim
t$, if they agree from some ordinal
onward; that is, they agree on a tail segment $[\beta,\alpha)$ of $\alpha$. Let the mathematicians agree on a choice of representative
for each $\sim$-equivalence class. Now, suppose that the hats are given
out. Each mathematician (except the last one, in the case that $\alpha$ is a successor ordinal) is able to observe a tail segment of the
actual assignment given, and thus knows the $\sim$-class of the actual
assignment. Let the mathematician at any particular position $\gamma$ compare the observed assignment beyond
$\gamma$ with the assignment of the pre-chosen representative from
that class. If they agree perfectly beyond $\gamma$, then let
mathematician $\gamma$ announce the color of the hat that he
or she would wear according to the chosen representative assignment.
Otherwise, mathematician $\gamma$ observes some
errors at positions beyond $\gamma$. Let $\beta$ be the supremum
of the positions of these errors, so that $\gamma<\beta$ but also
$\beta<\alpha$ since the observed assignment definitely agrees
with the representative from some point on. In this case, let mathematician $\gamma$ ignore the part of the assignment
beyond $\beta$, and instead use the fixed strategy for the game of
assignments of length $\beta$, using only the information about the hats up to $\beta$.
Notice that if $\beta$ is the supremum of the places where the
actual assignment differs from the representative, then everyone
beyond $\beta$ will guess correctly, and everyone before $\beta$
will compute $\beta$ correctly and therefore use the agreed-upon strategy for
the length $\beta$ game. So by the induction hypothesis, only
finitely many will be wrong. QED
Let me also describe another strategy, in the style of Alan Taylor, from what I
recall from a talk he gave at our seminar in New York several
years ago. See also Christopher S. Hardin and Alan D. Taylor, A Peculiar Connection Between the Axiom of Choice and Predicting the Future, which was mentioned in the comments.
We prove directly that there is a strategy for $\alpha$ many
mathematicians. First of all, let the mathematicians agree upon a
fixed well-ordering $\triangleleft$ of the space of all hat
$\alpha$-assignments. Now, suppose the hats are given out. Let
each mathematician observe the portion of the hat assignment given
to the mathematicians ahead, and let each mathematician compute
the $\triangleleft$-least total assignment that agrees with the
portion of the actual assignment that they observe. Each
mathematician should predict that their own hat color is the same
as it in in the $\triangleleft$-least assignment that they compute.
We now argue that only finitely many mathematicians are wrong. The
main point is that if $\gamma<\beta$, then the
$\triangleleft$-least assignment that mathematician $\gamma$
computes is at least as high in the $\triangleleft$ order as the
$\triangleleft$-least assignment that mathematician $\beta$
computes, since mathematician $\gamma$ observes all the information that $\beta$ observes and more about the actual assignment of hats. That is, as you move up higher in the mathematicians,
the computed $\triangleleft$-least approximation can only move down in the
$\triangleleft$ order if it changes. Every time there is an incorrect guess as we move up in the mathematicians, we
drop strictly lower in the $\triangleleft$-well-ordering. And since $\triangleleft$ is a well-order, this can happen only
finitely many times. Thus, only finitely many mathematicians guess
The argument is extremely general, and leads to the conclusion
that in any partial order, where the mathematicians are looking upward, then the collection of incorrect guesses forms a converse well-founded subset. And one can even generalize further than this, as Hardin and Taylor do.