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An efficient approach to chiral fullerene derivatives by catalytic enantioselective 1,3-dipolar cycloadditions

Nature Chemistry volume 1, pages 578–582 (2009)Cite this article

Abstract

Fullerene chirality is an important but undeveloped issue of paramount interest in fields such as materials science and medicinal chemistry. So far, enantiopure fullerene derivatives have been made from chiral starting materials or obtained by separating racemic mixtures. Here, we report the enantioselective catalytic synthesis of chiral pyrrolidinofullerenes (the most widely studied fullerene derivatives), which proceeds in high yields under very mild conditions at low temperatures. The combination of a particular metal catalyst—Ag(I) or Cu(II)—and a chiral ligand is able to direct the cycloaddition of buckminsterfullerene C60, the first non-coordinating dipolarophile used in such reactions, to opposite enantiofaces of N-metallated azomethine ylides. This methodology has proven to be quite general, affording enantiomeric excesses of greater than 90%. Furthermore, well-defined chiral carbon atoms linked to the fullerene sphere are able to perturb the inherent symmetry of the fullerene π-system as revealed by circular dichroism measurements.

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Figure 1: N-metallated azomethine ylide complexes, prepared from a chiral ligand, a metal salt, an imino-ester and a base, are able to cycloadd to a non-coordinating dipolarophile such as the all-carbon sphere C60.
Figure 2: Catalytic metal–ligand complexes allow the cycloaddidion of the iminoesters 1a–g to C60 under mild conditions.
Figure 3: Circular dichroism and UV spectra of fulleropyrrolidines 2a–d (concentration, 4 × 10−4 M in toluene).
Figure 4: Proposed concerted versus stepwise mechanism for the stereochemical outcome observed from the metal–ligand–iminoester complex.

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Acknowledgements

This work was supported by the MICINN of Spain (project CT2008-00795/BQU and Consolider-Ingenio 2010C-07-25200) and the CAM (project P-PPQ-000225-0505). S.F. thanks the MICINN for a Ramón y Cajal contract, and E.E.M. thanks the MICINN for a Doctoral Fellowship.

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Authors and Affiliations

  1. Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, Ciudad Universitaria s/n, Madrid, 28040, Spain

    Salvatore Filippone, Enrique E. Maroto, Ángel Martín-Domenech, Margarita Suarez & Nazario Martín

  2. Laboratorio de Síntesis Orgánica, Facultad de Química, Universidad de la Habana, La Habana, 10400, Cuba

    Margarita Suarez

  3. IMDEA- Nanociencia, Campus de la Universidad Autónoma de Madrid, Madrid, 28049, Spain

    Nazario Martín

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  1. Salvatore Filippone
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  2. Enrique E. Maroto
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  3. Ángel Martín-Domenech
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Contributions

N.M. and S.F. conceived and designed the experiments; E.M. and M.S. performed the experiments; A.M. analysed the data; N.M. and S.F. co-wrote the paper. All authors discussed the results and commented on the manuscript.

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Correspondence to Nazario Martín.

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Filippone, S., Maroto, E., Martín-Domenech, Á. et al. An efficient approach to chiral fullerene derivatives by catalytic enantioselective 1,3-dipolar cycloadditions. Nature Chem 1, 578–582 (2009). https://doi.org/10.1038/nchem.361

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