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Anion-π Catalysis Enabled by the Mechanical Bond.

ABSTRACT: We report a series of rotaxane-based anion-π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis.

SUBMITTER: Maynard JRJ

PROVIDER: S-EPMC9303940 | biostudies-literature | 2022 Mar

REPOSITORIES: biostudies-literature

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Anion-π Catalysis Enabled by the Mechanical Bond.

Maynard John R J JRJ Galmés Bartomeu B Stergiou Athanasios D AD Symes Mark D MD Frontera Antonio A Goldup Stephen M SM

Angewandte Chemie (International ed. in English) 20220203 12

We report a series of rotaxane-based anion-π catalysts in which the mechanical bond between a bipyridine macrocycle and an axle containing an NDI unit is intrinsic to the activity observed, including a [3]rotaxane that catalyses an otherwise disfavoured Michael addition in >60 fold selectivity over a competing decarboxylation pathway that dominates under Brønsted base conditions. The results are rationalized by detailed experimental investigations, electrochemical and computational analysis. ...[more]

PMID: 35040543

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