Extended Dynamic Mode Decomposition (EDMD) is a data-driven tool for forecasting and model reduction of dynamics, which has been extensively taken up in the physical sciences. While the method is conceptually simple, in deterministic chaos it is unclear what its properties are or even what it converges to. In particular, it is not clear how EDMD's least-squares approximation treats the classes of differentiable functions on which chaotic systems act. We develop for the first time a general, rigorous theory of EDMD on the simplest examples of chaotic maps: analytic expanding maps of the circle. To do this, we prove a new, basic approximation result in the theory of orthogonal polynomials on the unit circle (OPUC) and apply methods from transfer operator theory. We show that in the infinite-data limit, the least-squares projection error is exponentially small for trigonometric polynomial observable dictionaries. As a result, we show that forecasts and Koopman spectral data produced using EDMD in this setting converge to the physically meaningful limits, exponentially fast with respect to the size of the dictionary. This demonstrates that with only a relatively small polynomial dictionary, EDMD can be very effective, even when the sampling measure is not uniform. Furthermore, our OPUC result suggests that data-based least-squares projection may be a very effective approximation strategy more generally.