Catalytic asymmetric amination of N-nonsubstituted α-alkoxycarbonyl amides: Concise enantioselective synthesis of mycestericina F and G

Farouk Berhal, Sho Takechi, Naoya Kumagai, Masakatsu Shibasaki

Research output: Contribution to journalArticlepeer-review

36 Citations (Scopus)

Abstract

In an attempt to explore the synthetic utility of a ternary asymmetric catalyst comprising La(NO3)3·6H2O, amide-based ligand (R)-L1, and D-valine tert-butyl ester H-D-Val-OtBu, we investigated a catalytic, asymmetric amination of functionalized N-nonsubstituted α-alkoxycarbonyl amides using di-tert-butyl azodicarboxylate as an electrophilic aminating reagent. A highly functionalized, cyclic N-nonsubstituted α-alkoxycarbonyl amide delivered the desired amination product in up to 96% enantiometric excess, with the requisite functionalities of the polar heads of sphingosines with the appropriate stereochemical arrangement. The rapid asymmetric assembly of these functional groups allowed a concise enantioselective synthetic route to sphingosines to be established with a broad flexibility towards derivative synthesis. These studies have culminated in an efficient catalytic enantioselective total synthesis of immunosuppressive fungal metabolites mycestericina F (3a) and G (3b).

Original languageEnglish
Pages (from-to)1915-1921
Number of pages7
JournalChemistry - A European Journal
Volume17
Issue number6
DOIs
Publication statusPublished - 2011 Dec 7
Externally publishedYes

Keywords

  • amide-based ligands
  • asymmetric catalysis
  • asymmetric synthesis
  • cooperative effects
  • natural products

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

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