Tandem catalytic allylic amination and [2,3]-stevens rearrangement of tertiary amines

Arash Soheili, Uttam K. Tambar

Research output: Contribution to journalArticle

36 Citations (Scopus)

Abstract

We have developed a catalytic allylic amination involving tertiary aminoesters and allylcarbonates, which is the first example of the use of tertiary amines as intermolecular nucleophiles in metal-catalyzed allylic substitution chemistry. This process is employed in a tandem ammonium ylide generation/[2,3]-rearrangement reaction, which formally represents a palladium-catalyzed Stevens rearrangement. Low catalyst loadings and mild reaction conditions are compatible with an unprecedented substrate scope for the ammonium ylide functionality, and products are generated in high yields and diastereoselectivities. Mechanistic studies suggested the reversible formation of an ammonium intermediate.

Original languageEnglish (US)
Pages (from-to)12956-12959
Number of pages4
JournalJournal of the American Chemical Society
Volume133
Issue number33
DOIs
StatePublished - Aug 24 2011

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Amination
Nucleophiles
Ammonium Compounds
Palladium
Amines
Substitution reactions
Catalysts
Substrates
Metals

ASJC Scopus subject areas

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

Cite this

Tandem catalytic allylic amination and [2,3]-stevens rearrangement of tertiary amines. / Soheili, Arash; Tambar, Uttam K.

In: Journal of the American Chemical Society, Vol. 133, No. 33, 24.08.2011, p. 12956-12959.

Research output: Contribution to journalArticle

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