Anion-π catalysis on carbon allotropes

Beilstein J Org Chem. 2023 Dec 12:19:1881-1894. doi: 10.3762/bjoc.19.140. eCollection 2023.

Abstract

Anion-π catalysis, introduced in 2013, stands for the stabilization of anionic transition states on π-acidic aromatic surfaces. Anion-π catalysis on carbon allotropes is particularly attractive because high polarizability promises access to really strong anion-π interactions. With these expectations, anion-π catalysis on fullerenes has been introduced in 2017, followed by carbon nanotubes in 2019. Consistent with expectations from theory, anion-π catalysis on carbon allotropes generally increases with polarizability. Realized examples reach from enolate addition chemistry to asymmetric Diels-Alder reactions and autocatalytic ether cyclizations. Currently, anion-π catalysis on carbon allotropes gains momentum because the combination with electric-field-assisted catalysis promises transformative impact on organic synthesis.

Keywords: Diels–Alder reactions; anion–π interactions; autocatalysis; carbon nanotubes; catalysis; electric-field-induced catalysis; electromicrofluidics; enolate addition; ether cyclizations; fullerenes.

Publication types

  • Review

Grants and funding

We thank the University of Geneva, the National Centre of Competence in Research (NCCR) Molecular Systems Engineering (51NF40-205608) and the Swiss NSF for financial support (Excellence Grant 200020 204175; Swiss-ERC Advanced Grant TIMEUP, TMAG-2_209190).