The regioselective functionalization of C60 remains challenging, while the enantioselective functionalization of C60 is difficult to explore due to the need for complex chiral tethers or arduous chromatography. Metal–organic cages have served as masks to effect the regioselective functionalization of C60. However, it is difficult to control the stereochemistry of the resulting fullerene adducts through this method. Here we report a means of defining up to six stereocentres on C60, achieving enantioselective fullerene functionalization. This method involves the use of a metal–organic cage built from a chiral formylpyridine. Fullerenes hosted within the cavity of the cage can be converted into a series of C60 adducts through chemo-, regio- and stereo-selective Diels–Alder reactions with the edges of the cage. The chiral formylpyridine ultimately dictates the stereochemistry of these chiral fullerene adducts without being incorporated into them. Such chiral fullerene adducts may become useful in devices requiring circularly polarized light manipulation.
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All data supporting the findings of this study are included within the Article and its Supplementary Information, and are also available from the corresponding author on request. Crystallographic data for the structures reported in this paper have been deposited at the Cambridge Crystallographic Data Centre, under the deposition numbers 24124135 (ΛΛΛΛ-1), 24124134 (ΔΛΛΛ-C60·2) and 24124133 (PCBM·2′). Copies of these data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif. Source data are provided with this paper.
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This work was supported by the Engineering and Physical Sciences Research Council (EPSRC, EP/P027067/1) and the European Research Council (695009). Z.L. acknowledges the Cambridge Trust and China Scholarship Council for PhD funding. A.W.H. is the recipient of an Astex Pharmaceuticals Sustaining Innovation Post-Doctoral Award. S.F. acknowledges funding from the Engineering and Physical Sciences Research Council (EPSRC, UK) through an EPSRC Doctoral Prize Fellowship. We thank Diamond Light Source for beamtime on Beamline I19 (CY21497). We also thank the Yusuf Hamied Department of Chemistry NMR facility for characterization data and C. Fuertes-Espinosa for helpful discussions.
The authors declare no competing interests.
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Supplementary Figs. 1–111.
Supplementary Data 1
Crystallographic data for ΛΛΛΛ-1; (CCDC reference 24124135).
Supplementary Data 2
Crystallographic data for ΔΛΛΛ-C60·2; (CCDC reference 24124134).
Supplementary Data 3
Crystallographic data for PCBM·2′; (CCDC reference 24124133).
Supplementary Data 4
Statistical Source data for Supplementary Information.
Source Data Fig. 1
Statistical Source Data.
Source Data Fig. 4
Statistical Source Data.
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Lu, Z., Ronson, T.K., Heard, A.W. et al. Enantioselective fullerene functionalization through stereochemical information transfer from a self-assembled cage. Nat. Chem. 15, 405–412 (2023). https://doi.org/10.1038/s41557-022-01103-y