Paramagnetic 1H-NMR relaxation probes of stereoselectivity in metalloporphyrin catalyzed olefin epoxidation

John Taylor Groves, Stephen J. Crowley, Kirill V. Shalyaev

Research output: Contribution to journalArticle

23 Scopus citations

Abstract

Enantioselective catalytic epoxidation of olefins is an important problem from both practical and mechanistic points of view. The origins of chiral induction by asymmetric porphyrin and salen complexes were investigated by FT-NMR T1 relaxation techniques. A new chiral vaulted porphyrin (1) that carries (S)-binaphthyl-L-alanine straps across both faces of the porphyrin macrocycle was synthesized and characterized. (R)-styrene oxide was obtained in >9096 ee in the initial stages of styrene epoxidation with F5PhIO catalyzed by 1-Fe(III)C1. The transition state for olefin epoxidation with high-valent metal-oxo species was modeled by coordinating epoxides to paramagnetic copper complexes of the corresponding ligands. The epoxide enantiomer that better fit the chiral cavity of the catalyst, as revealed by T1 relaxation measurements, was also the major product of catalytic olefin epoxidation. These results are consistent with the 'lock- and-key' mechanism of asymmetric catalysis by metalloporphyrins. The copper complex of a chiral salen ligand showed no differentiation in terms of T1 relaxation rates between the enantiomers of cis-β-methylstyrene oxide in contrast to the high enantioselectivity observed for catalytic epoxidation.

Original languageEnglish (US)
Pages (from-to)106-119
Number of pages14
JournalChirality
Volume10
Issue number1-2
DOIs
StatePublished - 1998

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Catalysis
  • Pharmacology
  • Drug Discovery
  • Spectroscopy
  • Organic Chemistry

Keywords

  • Asymmetric catalysis
  • Chiral
  • Enantioselective
  • Mechanism
  • Oxidation
  • Porphyrin

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