Spirocyclic frameworks, polycyclic structures in which two rings share a single carbon atom, constitute key structural motifs across diverse areas, including optoelectronic and hole-transporting materials1–3, ligand design for coordination complexes4–6, and numerous natural products7. In a spiro skeleton, the two molecular units adopt an orthogonal arrangement, generating a rigid three-dimensional (3D) architecture. Introducing a single carbon atom to join two components to form the spiro centre therefore represents a direct strategy for constructing such frameworks. Previous carbon-atom-transfer approaches have largely relied on π-bond reactivity, whereas controlled insertion of a carbon atom into C–C σ-bonds remains challenging8–11. Here we report a rhodium-catalysed spiro-carbon-atom insertion reaction that converts biphenylene substrates into spirocyclic structures through sequential C–C bond activation. Using N-isocyanoiminophosphorane (PINC)12–14 as an atomic carbon equivalent, the reaction forms four new C–C bonds at a spiro centre. The transformation enables both homo- and cross-spirofusion of biphenylenes and can be extended to reactions combining σ- and π-bond activation. These results establish a catalytic strategy for constructing structurally complex spirocyclic frameworks through C–C σ-bond activation, with a single carbon atom serving as a central linchpin.
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Authors and Affiliations
Department of Applied Chemistry, Graduate School of Engineering, The University of Osaka, Suita, Osaka, Japan
Hayato Fujimoto, Masayuki Mizutani, Kazuya Imachi, Teruki Nishioka, Reona Ikeda & Mamoru Tobisu
Innovative Catalysis Science Division, Institute for Open and Transdisciplinary Research Initiatives (ICS-OTRI), The University of Osaka, Suita, Osaka, Japan
Hayato Fujimoto & Mamoru Tobisu
Corresponding authors
Correspondence to Hayato Fujimoto or Mamoru Tobisu.
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Supplementary Sections 1–19, including Supplementary Figs 1–3 and Supplementary Tables 1 and 2 – see contents for details.
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Fujimoto, H., Mizutani, M., Imachi, K. et al. Catalytic transfer of carbon atoms enables spirofusion of C–C σ-bonds. Nature (2026). https://doi.org/10.1038/s41586-026-11242-8
DOIhttps://doi.org/10.1038/s41586-026-11242-8
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