A great effort is currently being made in the field of electronics to replace classical inorganic solid-state materials (metals, silicon) by lightweight, mechanically flexible and highly tunable organic polymers (“organic electronics”). During the past decade, it has been recognized that the incorporation of main-group elements other than carbon into organic p-electron materials is a powerful approach to improve the optical and electronic properties of the parent systems. Boron has lately moved to the center stage of elements used as dopants in organic electronics, which has sparked vibrant interest in the development of efficient synthetic pathways to organoborane polymers. Recently, a spontaneous ring-opening reaction was discovered, providing convenient access to boron-containing building blocks for the synthesis of optoelectronic materials. The elucidation of the mechanistic details of this reaction required a close collaboration between experimentally oriented and computational chemists.