Managing highly coordinative substrates in asymmetric catalysis: A catalytic asymmetric amination with a lanthanum-based ternary catalyst

Tomoyuki Mashiko, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

84 Citations (Scopus)

Abstract

Full details of a catalytic asymmetric amination with a lanthanum/amide-based ligand catalyst system are described. A catalyst comprising La(NO3)3·6H2O, (R)-3a and H-D-Val-OtBu was identified to promote the catalytic asymmetric amination of nonprotected succinimide derivative 1 with as little as 1 mol % catalyst loading. Mechanistic studies by various spectroscopic analyses and several control and kinetic experiments suggested that the catalyst components were in equilibrium between the associated and dissociated forms, and that the reaction likely proceeded through a La(NO3)3· 6H2O/(R)-3a/H-D-Val-OtBu ternary complex. This catalyst system was also effective for asymmetric amination of N-nonsubstituted α-alkoxycarbonyl amides 7, hitherto unprecedented substrates in asymmetric catalysis, probably due to their attenuated reactivity and difficult stereocontrol, affording the amination products in up to >99% yield and >99% ee. The high catalytic performance and enantiocontrol of the reaction with highly coordinative substrates were achieved by the activation/recognition of the substrates exerted by coordination to lanthanum and hydrogen bonding cooperatively in the transition state.

Original languageEnglish
Pages (from-to)14990-14999
Number of pages10
JournalJournal of the American Chemical Society
Volume131
Issue number41
DOIs
Publication statusPublished - 2009 Oct 21
Externally publishedYes

ASJC Scopus subject areas

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

Fingerprint

Dive into the research topics of 'Managing highly coordinative substrates in asymmetric catalysis: A catalytic asymmetric amination with a lanthanum-based ternary catalyst'. Together they form a unique fingerprint.

Cite this