Copper-nitrenoid formation and transfer in catalytic olefin aziridination utilizing chelating 2-pyridylsulfonyl moieties.
We have developed an efficient protocol for copper-catalyzed olefin aziridination using 5-methyl-2-pyridinesulfonamide or 2-pyridinesulfonyl azide as the nitrenoid source. The presence of a 2-pyridyl group significantly facilitates aziridination, suggesting that the reaction is driven by the favorable formation of a pyridyl-coordinated nitrenoid intermediate. Using this chelation-assisted strategy, synthetically acceptable yields of aziridines could be obtained with a range of aryl olefins even in the absence of external ligands. Importantly, a large excess of olefin is not required. X-ray crystallography, ESI-MS, Hammett plot analysis, kinetic studies, and computational undertakings strongly support that the observed aziridination is driven by internal coordination.
Han
Hoon
H
Center for Molecular Design and Synthesis, Department of Chemistry and School of Molecular Science (BK21), Korea Advanced Institute of Science and Technology, Daejon 305-701, Korea.
Park
Seong Byeong
SB
Kim
Sang Kyu
SK
Chang
Sukbok
S
D000475:Alkenes / Q000737:chemistry*; D001388:Aziridines / Q000138:chemical synthesis* / Q000737:chemistry; D002384:Catalysis; D003300:Copper / Q000737:chemistry*; D018360:Crystallography, X-Ray; D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry*; D008958:Models, Molecular; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism; D013450:Sulfones / Q000737:chemistry*
D000475:Alkenes; D001388:Aziridines; D007097:Imines; D009942:Organometallic Compounds; D011725:Pyridines; D013450:Sulfones; D003300:Copper