We propose the multiple reflection expansion as a tool for the calculation of heat kernel coefficients. As an example, we give the coefficients for a sphere as a finite sum over reflections, obtaining as a byproduct, a relation between the coefficients for Dirichlet and Neumann boundary conditions. Further, we calculate the heat kernel coefficients for the most general matching conditions on the surface of a sphere, including those cases corresponding to the presence of delta and delta prime background potentials. In the latter case, the multiple reflection expansion is shown to be nonconvergent.