A celebrated result of Karpelevi\v c describes $Θ_n,$ the collection of all eigenvalues arising from the stochastic matrices of order $n.$ The boundary of $Θ_n$ consists of roots of certain one-parameter families of polynomials, and those polynomials are naturally associated with the so--called reduced Ito polynomials of Types 0, I, II and III. In this paper we explicitly characterise all $n \times n$ stochastic matrices whose characteristic polynomials are of Type 0 or Type I, and all sparsest stochastic matrices of order $n$ whose characteristic polynomials are of Type II or Type III. The results provide insights into the structure of stochastic matrices having extreme eigenvalues.