Usually, the phase space of a physical system is defined as the cotangent bundle of the configuration space at some fixed time slice $t = t_0$, conveniently co-ordinatized by $\{q^a, p_a\}$ where $$ p_a = \frac{\partial \mathcal{L}}{\partial \dot{q}^a}. $$
This $p$ co-ordinates (called canonical momenta) are convenient, because the symplectic structure on the phase space is of very simple form: $$ \left\{ q^a, p_b \right\} = \delta^a_b, \\ \{q,q\}=\{p,p\}=0. $$
A moment of reflection will convince you that the phase space is nothing more than the space of solutions of the equations of motion, together with a suitable topology making it into a differential manifold.
This second definition seems far more natural and far-reaching than the first one: it makes sense even in exotic cases, e.g. with degenerate Hessian, with discrete time, with non-determinism of the equations of motion, etc. Also, this definition does not single out a specific value of the time parameter $t = t_0$, thus making independence of $t_0$ in the canonical formalism manifest. In fact I would go further and say that this second definition does not make any assumptions about existence of time at all!
I would like to understand how to define the symplectic structure (the Poisson bracket) for this second definition of the phase space, and to which extend it is possible.
I expect this structure to be generated by the action functional $$ S(t_i, t_f) = \intop_{t_i}^{t_f} dt \mathcal{L} $$ taken as a function of phase space (i.e. a function on the space of solutions to the equations of motion, parametrized by $t_i$ and $t_f$).
However, I don't know how to write the general definition of the Poisson bracket between two functions of the phase space, defined by the action functional.