The difficulty of accessing belt molecules lies in the final ringclosing step in which a particular precursor forms the highly strained belt structures. Thus, available synthetic strategies are rather limited. In our previous work, fully fused carbon nanobelts 10a,b were synthesized via intramolecular reductive or oxidative C-C bond-forming reactions in the final annulation step (Figure , top). On the other hand, the strategy of inserting belt components intermolecularly during annulation events (Figure 2, bottom) has not yet been studied, although this approach has potential benefits regarding substrate flexibility and variety. Based on the recent progress in Buchwald-Hartwig amination reactions, we speculated an intermolecular synthetic strategy for N-doped belt synthesis via annulative C-N bond formation reactions of zigzag macrocycles. Thus, we envisioned that the Z-stilbenebased macrocycle 1 could afford the target N-doped aromatic belt 2 in one step by the 12-fold annulative Buchwald-Hartwig reactions (or the so-called annulative double N-arylation reactions 12 ). Z-stilbene-based macrocyclic precursor 1 was prepared following our previous report. 10a Next, palladium-catalyzed amination reactions between 1 and aniline were performed. In the first attempt, debrominated, hydroaminated, and over-/lessaminated ring products were detected by mass spectrometry but not the desired belt molecules. Subsequently, various amines were screened, aiming at the reduction of these undesired products. Through this screening, it was found that pmethoxyaniline afforded the desired belt molecule 2, probably because the electron-donating methoxy groups promoted the reductive elimination and helped overcome the belt strain. Among the various conditions tested, Pd(dba)2 (dba = dibenzylideneacetone) and PMe( t Bu)2•HBF4 salt as the catalyst and ligand, respectively, furnished the desired compound most efficiently. In particular, the reaction between 1 and pmethoxyaniline using 60 mol% Pd(dba)2, 120 mol% PMe( t Bu)2•HBF4, and 30 equivalents (equiv.) of NaO t Bu in mxylene at 140 °C for 8 h provided 2 in 2.3% isolated yield (Scheme 1). The structure of nanobelt 2 was fully characterized by 1 H and C NMR spectroscopies, MALDI-TOF MS, and X-ray diffraction.