Next-generation synoptic photometric surveys will yield unprecedented (for the astronomical community) volumes of data and the processes of discovery and rare-object identification are, by necessity, becoming more autonomous. Such autonomous searches can be used to find objects of interest applicable to a wide range of outstanding problems in astronomy, and in this paper we present the methods and results of a largely autonomous search for highly eccentric detached eclipsing binary systems in the Machine-learned All-Sky Automated Survey Classification Catalog. 106 detached eclipsing binaries with eccentricities of e gtrsim 0.1 are presented, most of which are identified here for the first time. We also present new radial- velocity curves and absolute parameters for six of those systems with the long-term goal of increasing the number of highly eccentric systems with orbital solutions, thereby facilitating further studies of the tidal circularization process in binary stars.