The most concrete way to express the relation between Dirac matrices and homotopy groups of classical groups is given by the following construction.
Let (γμ)μ=1,…,d be n×n Dirac matrices (in Euclidean signature), i.e. satisfying
{γμ,γν}=2δμν
Then the map
Rd→Mn(C)
(xμ)μ=1,…,d↦∑dμ=1γμxμ
gives in restriction to the unit sphere ∑dμ=1(xμ)2=1 a map
Sd−1→GLn(C)
(indeed, in this case: (∑μγμxμ)(∑νγνxν)=∑dμ=1(xμ)2=1n).
Taking the homotopy class of this map, we get an element in πd−1(GLn(C))=πd−1(Un).
If the Dirac matrices are real, we get a map
Sd−1→GLn(R)
and so an element in πd−1(GLn(R))=πd−1(On).
We get a map from possible Dirac matrices to homotopy groups of unitary groups (or orthogonal groups). Up to appropriate equivalence on both sides, this is a one to one correspondence : see
http://www.maths.ed.ac.uk/~aar/papers/abs.pdf
for the precise (and original) statement. In particular, under this correspondence, Bott periodicity on the Dirac matrices side matches with Bott periodicity on the homotopy groups side.
For a physical interpretation in the context of D-branes, see https://arxiv.org/abs/hep-th/9810188