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Photoinduced dual bond rotation of a nitrogen-containing system realized by chalcogen substitution

Nature Chemistry (2024)Cite this article

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Abstract

Photoinduced concerted multiple-bond rotation has been proposed in some biological systems. However, the observation of such phenomena in synthetic systems, in other words, the synthesis of molecules that undergo photoinduced multiple-bond rotation upon photoirradiation, has been a challenge in the photochemistry field. Here we describe a chalcogen-substituted benzamide system that exhibits photoinduced dual bond rotation in heteroatom-containing bonds. Introduction of the chalcogen substituent into a sterically hindered benzamide system provides sufficient kinetic stability and photosensitivity to enable the photoinduced concerted rotation. The presence of two different substituents on the phenyl ring in the thioamide derivative enables the generation of a pair of enantiomers and E/Z isomers. Using these four stereoisomers as indicators of which bonds are rotated, we monitor the photoinduced C–N/C–C concerted bond rotation in the thioamide derivative depending on external stimuli such as temperature and photoirradiation. Theoretical calculations provide insight on the mechanism of this selective photoinduced C–N/C–C concerted rotation.

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Fig. 1: Photoinduced multiple-bond rotation.
Fig. 2: Rotational barriers of C–N axis of ortho-disubstituted tertiary benzamides.
Fig. 3: Photoinduced isomerization of the chalcogen amides.
Fig. 4: Separation and stereochemical determination of each isomer.
Fig. 5: Different rotational mode of the thioamide system.
Fig. 6: Quantum chemical calculation for the reaction mechanism of the photoinduced isomerization of 8-S.

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Data availability

The authors declare that the data supporting the findings of this study are available within the paper and its Supplementary Information files. Supplementary Data 1 contains the cartesian coordinates for the calculated structures. Source data are provided with this paper.

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Acknowledgements

This research was supported in part by JSPS KAKENHI Grant-in-Aid for Challenging Research (Exploratory) (S.I., grant number JP18K19384), Grant-in-Aid for Scientific Research (B) (T.T., grant number JP18K19384), Grant Platform Project for Supporting Drug Discovery and Life Science Research (Basis for Supporting Innovative Drug Discovery and Life Science Research (BINDS)) from AMED (S.I., grant number JP22ama121039) a Grant-in-Aid for Challenging Research (Exploratory) (Y.H., 22K19002), JST-FOREST (Y.H.), JST-ERATO (S.M. and Y.H., JPMJER1903), and JSPS-WPI and The Akiyama Life Science Foundation (A.K.), and was partly supported by Hokkaido University, Global Facility Center (GFC), Pharma Science Open Unit (PSOU), funded by MEXT under ‘Support Program for Implementation of New Equipment Sharing System’. Part of the results was computed at the supercomputer system at the information initiative centre in Hokkaido University. We thank T. Mita (Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Japan) and Y. Inokuma (Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Japan) for helpful discussion on the photochemistry. We thank M. Jin (Institute for Chemical Reaction Design and Discovery (WPI-ICReDD)) for helpful discussion and providing instrument for quantum yield determination.

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Authors and Affiliations

  1. Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo, Japan

    Shotaro Nagami, Rintaro Kaguchi, Taichi Akahane, Satoshi Ichikawa & Akira Katsuyama

  2. Institute for Chemical Reaction Design and Discovery (WPI-ICReDD), Hokkaido University, Sapporo, Japan

    Yu Harabuchi & Satoshi Maeda

  3. JST, ERATO, Maeda Artificial Intelligence in Chemical Reaction Design and Discovery Project, Sapporo, Japan

    Yu Harabuchi & Satoshi Maeda

  4. Department of Chemistry, Faculty of Science, Hokkaido University, Sapporo, Japan

    Yu Harabuchi & Satoshi Maeda

  5. Frontier Research Center of Advanced Material and Life Science, Faculty of Advanced Life Science, Hokkaido University, Sapporo, Japan

    Tohru Taniguchi & Kenji Monde

  6. Global Institution for Collaborative Research and Education, Hokkaido University, Sapporo, Japan

    Satoshi Ichikawa & Akira Katsuyama

  7. Center for Research and Education on Drug Discovery, Faculty of Pharmaceutical Sciences, Hokkaido University, Sapporo, Japan

    Satoshi Ichikawa & Akira Katsuyama

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Contributions

A.K. and. S.I. designed the research and A.K., R.K and S.I designed the experiments. A.K., Y.H. and S.M. performed calculation. S.N., R.K. and T.A. prepared compounds, acquired experimental data for the isomerization and measured the UV spectra. S.N., T.A. and A.K. analysed experimental data for the isomerization. T.T. and K.M. measured the VCD spectra. S.N., A.K., R.K., T.A., Y.H., T.T., K.M., S.M. and S.I. wrote the paper. All authors discussed the results and commented on the paper and have given approval to the final version of the manuscript.

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Correspondence to Satoshi Ichikawa or Akira Katsuyama.

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Extended data

Extended Data Fig. 1 Photo-induced isomerization of the chalcogen amides.

a, Kinetic parameters of the Z to E isomerization. Means and standard deviations are shown for three independent experiments. The variations from the standard condition were also shown. b, Kinetics of the racemization under the photochemical conditions. Means and standard deviations are shown for three independent experiments.

Extended Data Fig. 2 Thermal or photoinduced isomerization of two isomers of 1-S.

a, The time courses of the isomerization of the Z-(R)-1-S under a thermal condition. The circles indicate experimental ratio of each isomer at each time, and the dotted lines connect adjacent points. b, The time courses of the photo-induced isomerization of the Z-(S)-1-S. Three individual experiments were performed, and the representative data are presented. The circles indicate experimental ratio of each isomer at each time, and the dotted lines connect adjacent points.

Source data

Extended Data Fig. 3 Photoinduced isomerization of E-(R)-1-S.

Comparison of chiral HPLC chromatograms of isomerization after 2 minutes and 24 hours, and under oxygen atmosphere.

Source data

Extended Data Fig. 4 Quantum yields for the isomerization of E-(R)-7-S and Z-(S)-7-S.

a, Chiral HPLC chromatograms of isolated Z-(S)-7-S, Z-(R)-7-S, E-(S)-7-S and E-(R)-7-S. b, VCD spectra of each stereoisomer of 7-S. Absolute stereochemistry was determined by comparing theoretical and experimental spectra. c, Quantum yields were determined at 365 nm. Representative data are presented from the three individual experiments. Linear behavior was observed in the initial stage of the isomerization, and quantum yields were determined from the kinetics parameter. Means are shown for the three independent experiments.

Source data

Supplementary information

Supplementary Information

Supplementary Figs. 1–507, Tables 1–23, methods and discussion.

Supplementary Data 1

Cartesian coordinates for the calculated structures.

Source data

Source data for all figures and Extended Data figures

Raw data for Figs. 2–5 and Extended Data Figs 2–4.

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Nagami, S., Kaguchi, R., Akahane, T. et al. Photoinduced dual bond rotation of a nitrogen-containing system realized by chalcogen substitution. Nat. Chem. (2024). https://doi.org/10.1038/s41557-024-01461-9

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