Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis

Sean A. Reed, M. Christina White

Research output: Contribution to journalArticlepeer-review


A novel heterobimetallic Pd(II)sulfoxide/(salen)Cr(III)Cl-catalyzed intermolecular linear allylic C-H amination (LAA) is reported. This reaction directly converts densely functionalized α-olefin substrates (1 equiv) to linear (E)-allylic carbamates with good yields and outstanding regio- and stereoselectivities (>20:1). Chiral bis-homoallylic and homoallylic oxygen, nitrogen, and carbon substituted α-olefins undergo allylic C-H amination with good yields, excellent selectivities, and no erosion in enantiomeric purity. Streamlined routes to (E)-allylic carbamates that can be further elaborated to medicinally and biologically relevant allylic amines are also demonstrated. Valuable 15N-labeled allylic amines may be generated directly from allyl moieties at late stages of synthetic routes by using the readily available 15N-(methoxycarbonyl)-p-toluenesulfonamide nucleophile. Evidence is provided that this reaction proceeds via a heterobimetallic mechanism where Pd/sulfoxide mediates allylic C-H cleavage to form a π-allylPd intermediate, and (salen)Cr(III)Cl/BQ work together to promote functionalization with the nitrogen nucleophile.

Original languageEnglish (US)
Pages (from-to)3316-3318
Number of pages3
JournalJournal of the American Chemical Society
Issue number11
StatePublished - Mar 19 2008

ASJC Scopus subject areas

  • Catalysis
  • General Chemistry
  • Biochemistry
  • Colloid and Surface Chemistry


Dive into the research topics of 'Catalytic intermolecular linear allylic C-H amination via heterobimetallic catalysis'. Together they form a unique fingerprint.

Cite this