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Catalytic stereoselective synthesis of doubly, triply and quadruply twisted aromatic belts

Nature Synthesis volume 2, pages 888–897 (2023)Cite this article

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Abstract

Twisted aromatic belt molecules provide unique topologies and complex chiralities for nanocarbon materials. However, a synthetic method for aromatic belts with multiple twists remains elusive. Here we report the catalytic and stereoselective synthesis of doubly, triply and quadruply twisted aromatic belts (up to e.r. = 98:2) via rhodium(I)-catalysed asymmetric [2 + 2 + 2] cycloadditions. The hybrid substrate design, consisting of curved metaphenylene units and linear paraphenylene units, overcomes the hurdles of conventional methods, that is, large twist strain and unravelling of twists during belt formation, allowing the coexistence of multiple P- and M-twists in a single belt molecule. Three-dimensional structures of the multiply twisted aromatic belts were confirmed by X-ray crystallography, revealing that their topology depends on the sequence of P- and M-twists. Decomposition analysis of the linking number (Lk) shows that the twisting number (Tw) of the triply twisted Möbius belt is Tw = 2.45, among the highest Tw found for twisted conjugated macrocycles. Analysis of the electron density of delocalized bonds reveals that the electronic structure has unique Lk-dependent topologies, such as a catenane and a trefoil knot.

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Fig. 1: Precedents of double-stranded twisted belts.
Fig. 2: Synthetic strategy to introduce multiple twists in an aromatic belt.
Fig. 3: Catalytic stereoselective synthesis of multiply twisted aromatic belts.
Fig. 4: X-ray crystal structures of 10, 12 and 14.
Fig. 5: Molecular topologies and electronic structures of multiply twisted aromatic belts.
Fig. 6: Photophysical and chiroptical properties of aromatic belts.

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Data availability

The data that support the findings of this study are available in this article and its Supplementary Information (experimental procedures and characterization data). Crystallographic data for the structures reported in this article have been deposited at the Cambridge Crystallographic Data Centre, under deposition numbers CCDC 2220749 [(±)-10], CCDC 2220760 [(±)-12] and CCDC 2220761 (14). Copies of the data can be obtained free of charge via https://www.ccdc.cam.ac.uk/structures/.

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Acknowledgements

This research was supported partly by Grants-in-Aid for Scientific Research (numbers JP21K18949 and JP19H00893 to K.T., number JP21J22287 to J.N., number JP22H05346 to Y.N., number 20H02720 to K.M. and numbers 17H06173, 22H00320 and JP22H05125 to M.U.) from JSPS (Japan) and CREST (number JPMJCR19R2 to M.U.) from JST (Japan). We thank Takasago International Corporation for the gift of Segphos and H8-BINAP. A generous allotment of computational resources from TSUBAME (Tokyo Institute of Technology) is gratefully acknowledged.

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Authors and Affiliations

  1. Department of Chemical Science and Engineering, Tokyo Institute of Technology, Tokyo, Japan

    Juntaro Nogami, Yuki Nagashima & Ken Tanaka

  2. RIKEN Center for Emergent Matter Science (CEMS), Wako, Japan

    Daisuke Hashizume

  3. Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo, Japan

    Kazunori Miyamoto & Masanobu Uchiyama

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  1. Juntaro Nogami
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  2. Daisuke Hashizume
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  4. Kazunori Miyamoto
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Contributions

J.N. designed the project, carried out experimental works and wrote a draft manuscript. J.N. and Y.N. carried out computational studies. D.H. performed X-ray crystal structure analyses of triply and quadruply twisted aromatic belts 12 and 14. K.M. and M.U. performed an X-ray crystal structure analysis of doubly twisted aromatic belt 10. K.T. designed, advised and directed the project, and wrote the manuscript. All authors edited the manuscript.

Corresponding authors

Correspondence to Daisuke Hashizume or Ken Tanaka.

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Nature Synthesis thanks Juan Casado Cordon and the other, anonymous, reviewer(s) for their contribution to the peer review of this work. Primary handling editor: Alison Stoddart, in collaboration with the Nature Synthesis team.

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Supplementary information

Supplementary information

Synthetic experiments, chiral HPLC charts of 10, 12 and 13, X-ray crystallographic analyses of (±)-10, (±)-12 and 14, possible mechanism for stereoselective [2 + 2 + 2] cycloaddition, photophysical and chiroptical properties, DFT calculations, 1H, 13C and 2D NMR spectra of compounds, Supplementary Figs. 1–40 and Tables 1–36.

Supplementary Data 1

Crystal data for compound 10, CCDC 2220749.

Supplementary Data 2

Crystal data for compound 12, CCDC 2220760.

Supplementary Data 3

Crystal data for compound 14, CCDC 2220761.

Source data

Source Data Fig. 5

Statistical Source Data. xyz coordinate data and angular information used to calculate linking numbers for compounds 10, 12, 13, Möbius-type [10]CPP and triply twisted carbon nanobelt.

Source Data Fig. 6

Statistical Source Data. Raw data (.txt) of ultraviolet–visible absorption, fluorescence and ECD spectra of compounds 10, 11, 12, 13 and 14.

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Nogami, J., Hashizume, D., Nagashima, Y. et al. Catalytic stereoselective synthesis of doubly, triply and quadruply twisted aromatic belts. Nat. Synth 2, 888–897 (2023). https://doi.org/10.1038/s44160-023-00318-2

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