Catalytic asymmetric transannulation of NH-1,2,3-triazoles with olefins

Sen Wai Kwok, Li Zhang, Neil P. Grimster, Valery V. Fokin

Research output: Contribution to journalArticle

96 Citations (Scopus)

Abstract

A convenient one-pot asymmetric synthesis of 2,3-dihydropyrroles from in situ generated triflated triazoles and olefins is described that further expands the utility of azavinyl carbene chemistry and provides access to an important class of cyclic enamides. Mechanistic investigations support the involvement of triflated cyclopropylaldimine intermediates in the formation of 2,3-dihydropyrrole. To the best of our knowledge, this is the first example of a chiral Brønsted acid catalyzed rearrangement of cyclopropylimines into enantioenriched 2,3-dihydropyrroles. Enantioenriched dihydropyrroles can be generated by a rhodium(II)-catalyzed asymmetric transannulation between sulfonyl-1,2,3-triazoles and electron-rich styrenes. Mechanistic investigations support the formation of cyclopropane intermediates which undergo ring expansion to 2,3-dihydropyrroles in the presence of a chiral Brønsted acid catalyst.

Original languageEnglish
Pages (from-to)3452-3456
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number13
DOIs
Publication statusPublished - 24 Mar 2014
Externally publishedYes

Fingerprint

Triazoles
Alkenes
Olefins
Acids
Rhodium
Styrene
Styrenes
Catalysts
Electrons
pyrroline

Keywords

  • azavinyl carbenes
  • dihydropyrroles
  • enamides
  • rhodium
  • triazoles

ASJC Scopus subject areas

  • Chemistry(all)
  • Catalysis
  • Medicine(all)

Cite this

Catalytic asymmetric transannulation of NH-1,2,3-triazoles with olefins. / Kwok, Sen Wai; Zhang, Li; Grimster, Neil P.; Fokin, Valery V.

In: Angewandte Chemie - International Edition, Vol. 53, No. 13, 24.03.2014, p. 3452-3456.

Research output: Contribution to journalArticle

Kwok, Sen Wai ; Zhang, Li ; Grimster, Neil P. ; Fokin, Valery V. / Catalytic asymmetric transannulation of NH-1,2,3-triazoles with olefins. In: Angewandte Chemie - International Edition. 2014 ; Vol. 53, No. 13. pp. 3452-3456.
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