Curvulamine and related polypyrrole alkaloids represent a fascinating new class of natural products with unprecedented chemical structures, intriguing biological activities, and mysterious biosynthetic origins. Herein we report the first studies toward these molecules, resulting in a 10-step total synthesis of (-)-curvulamine, a dimeric member with promising Gram-positive and -negative antibiotic activity. A number of interesting chemical findings, including exploitation of the heteroaromatic pyrrolo[1,2-a]azepinone nucleus and an efficient stereodivergent reduction, are reported.