TY - JOUR
T1 - Direct stereospecific synthesis of unprotected N-H and N-Me aziridines from olefins
AU - Jat, Jawahar L.
AU - Paudyal, Mahesh P.
AU - Gao, Hongyin
AU - Xu, Qing Long
AU - Yousufuddin, Muhammed
AU - Devarajan, Deepa
AU - Ess, Daniel H.
AU - K̈urti, Lászĺo
AU - Falck, John R.
PY - 2014
Y1 - 2014
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84892747265&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84892747265&partnerID=8YFLogxK
U2 - 10.1126/science.1245727
DO - 10.1126/science.1245727
M3 - Article
C2 - 24385626
AN - SCOPUS:84892747265
SN - 0036-8075
VL - 343
SP - 61
EP - 65
JO - Science
JF - Science
IS - 6166
ER -