Twelve-fold dearomative esterification of (6,6)carbon nanobelt

Carbon nanobelts (CNBs), cyclic aromatic hydrocarbons with belt-shaped topologies, have growing interest as structurally unique and optoelectronically promising nanocarbons. Yet, strategies for their direct and site-selective functionalization remain scarce. Here we report a magnesium-mediated, multi-fold dearomative esterification of (6,6)CNB, enabling the installation of twelve ester groups in a single transformation. Single crystal X-ray structural analysis revealed regioselective dearomatization patterns, while mechanistic studies uncovered a radical-driven pathway involving oxyiminium intermediate generated in situ from alkyl chloroformates and amide solvents. Computational analysis further indicated that strain release in the CNB framework drives the high degree of functionalization. This methodology not only expands the synthetic toolbox for aromatic nanobelts but also allows tunable modulation of their host–guest properties via enhanced conformational flexibility.