Molybdenum-Catalyzed Asymmetric Hydrogenation of Fused Arenes and Heteroarenes

Peter Viereck, Gabriele Hierlmeier, Paolo Tosatti, Tyler P. Pabst, Kurt Puentener, Paul J. Chirik

Research output: Contribution to journalArticlepeer-review

Abstract

The synthesis of enantioenriched molybdenum precatalysts for the asymmetric hydrogenation of substituted quinolines and naphthalenes is described. Three classes of pincer ligands with chiral substituents were evaluated as supporting ligands in the molybdenum-catalyzed hydrogenation reactions, where oxazoline imino(pyridine) chelates were identified as optimal. A series of 2,6-disubstituted quinolines was hydrogenated to enantioenriched decahydroquinolines with high diastereo- and enantioselectivities. For quinoline derivatives, selective hydrogenation of both the carbocycle and heterocycle was observed depending on the ring substitution. Spectroscopic and mechanistic studies established molybdenum η6-arene complexes as the catalyst resting state and that partial hydrogenation arises from dissociation of the substrate from the coordination sphere of molybdenum prior to complete reduction. A stereochemical model is proposed based on the relative energies of the respective coordination of the prochiral faces of the arene determined by steric interactions between the substrate and the chiral ligand, rather than through precoordination by a heteroatom.

Original languageEnglish (US)
Pages (from-to)11203-11214
Number of pages12
JournalJournal of the American Chemical Society
Volume144
Issue number25
DOIs
StatePublished - Jun 29 2022

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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