Catalytic, Enantioselective syn-Diamination of Alkenes

Zhonglin Tao, Bradley B. Gilbert, Scott E. Denmark

Research output: Contribution to journalArticle

Abstract

The enantioselective, vicinal diamination of alkenes represents one of the stereocontrolled additions that remains an outstanding challenge in organic synthesis. A general solution to this problem would enable the efficient and selective preparation of widely useful, enantioenriched diamines for applications in medicinal chemistry and catalysis. In this article, we describe the first enantioselective, syn-diamination of simple alkenes mediated by a chiral, enantioenriched organoselenium catalyst together with a N,N′-bistosyl urea as the bifunctional nucleophile and N-fluorocollidinium tetrafluoroborate as the stoichiometric oxidant. Diaryl, aryl-alkyl, and alkyl-alkyl olefins bearing a variety of substituents are all diaminated in consistently high enantioselectivities but variable yields. The reaction likely proceeds through a Se(II)/Se(IV) redox catalytic cycle reminiscent of the syn-dichlorination reported previously. Furthermore, the syn-stereospecificity of the transformation shows promise for highly enantioselective diaminations of alkenes with no strong steric or electronic bias.

Original languageEnglish (US)
Pages (from-to)19161-19170
Number of pages10
JournalJournal of the American Chemical Society
Volume141
Issue number48
DOIs
StatePublished - Dec 4 2019

Fingerprint

alkene
Alkenes
Olefins
Bearings (structural)
catalysis
Synthetic Chemistry Techniques
oxidant
Nucleophiles
urea
Diamines
Pharmaceutical Chemistry
Enantioselectivity
catalyst
Catalysis
Oxidants
Urea
Oxidation-Reduction
Catalysts

ASJC Scopus subject areas

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

Cite this

Catalytic, Enantioselective syn-Diamination of Alkenes. / Tao, Zhonglin; Gilbert, Bradley B.; Denmark, Scott E.

In: Journal of the American Chemical Society, Vol. 141, No. 48, 04.12.2019, p. 19161-19170.

Research output: Contribution to journalArticle

Tao, Zhonglin ; Gilbert, Bradley B. ; Denmark, Scott E. / Catalytic, Enantioselective syn-Diamination of Alkenes. In: Journal of the American Chemical Society. 2019 ; Vol. 141, No. 48. pp. 19161-19170.
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