Direct stereospecific synthesis of unprotected N-H and N-Me aziridines from olefins

Jawahar L. Jat, Mahesh P. Paudyal, Hongyin Gao, Qing Long Xu, Muhammed Yousufuddin, Deepa Devarajan, Daniel H. Ess, Lászĺo K̈urti, John R. Falck

Research output: Contribution to journalArticlepeer-review

130 Scopus citations

Abstract

Despite the prevalence of the N-H aziridine motif in bioactive natural products and the clear advantages of this unprotected parent structure over N-protected derivatives as a synthetic building block, no practical methods have emerged for direct synthesis of this compound class from unfunctionalized olefins. Here, we present a mild, versatile method for the direct stereospecific conversion of structurally diverse mono-, di-, tri-, and tetrasubstituted olefins to N-H aziridines using O-(2,4-dinitrophenyl)hydroxylamine (DPH) via homogeneous rhodium catalysis with no external oxidants. This method is operationally simple (i.e., one-pot), scalable, and fast at ambient temperature, furnishing N-H aziridines in good-to-excellent yields. Likewise, N-alkyl aziridines are prepared from N-alkylated DPH derivatives. Quantum-mechanical calculations suggest a plausible Rh-nitrene pathway.

Original languageEnglish (US)
Pages (from-to)61-65
Number of pages5
JournalScience
Volume343
Issue number6166
DOIs
StatePublished - Jan 1 2014

ASJC Scopus subject areas

  • General

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